TWI537244B - Catalyst for metathesis of ethylene and 2-butene and/or double bond isomerization - Google Patents
Catalyst for metathesis of ethylene and 2-butene and/or double bond isomerization Download PDFInfo
- Publication number
- TWI537244B TWI537244B TW099122490A TW99122490A TWI537244B TW I537244 B TWI537244 B TW I537244B TW 099122490 A TW099122490 A TW 099122490A TW 99122490 A TW99122490 A TW 99122490A TW I537244 B TWI537244 B TW I537244B
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- Taiwan
- Prior art keywords
- butene
- catalyst
- isomerization
- metathesis
- ethylene
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims description 250
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 title claims description 162
- 238000006317 isomerization reaction Methods 0.000 title claims description 138
- 238000005649 metathesis reaction Methods 0.000 title claims description 102
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims description 74
- 239000005977 Ethylene Substances 0.000 title claims description 74
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 title claims description 73
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 228
- 238000006243 chemical reaction Methods 0.000 claims description 106
- 239000000395 magnesium oxide Substances 0.000 claims description 105
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 105
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 105
- 238000000034 method Methods 0.000 claims description 58
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 40
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 37
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 37
- 239000003381 stabilizer Substances 0.000 claims description 33
- 150000001336 alkenes Chemical class 0.000 claims description 29
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 29
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 29
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 26
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 24
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 20
- -1 C 4 alkane Chemical class 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000004508 fractional distillation Methods 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 2
- 238000005194 fractionation Methods 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 claims 1
- 239000012188 paraffin wax Substances 0.000 claims 1
- 230000032683 aging Effects 0.000 description 39
- 230000000694 effects Effects 0.000 description 36
- 230000009849 deactivation Effects 0.000 description 16
- 239000002245 particle Substances 0.000 description 14
- 239000011148 porous material Substances 0.000 description 14
- 230000008929 regeneration Effects 0.000 description 14
- 238000011069 regeneration method Methods 0.000 description 14
- 230000001186 cumulative effect Effects 0.000 description 13
- 238000005984 hydrogenation reaction Methods 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 238000005470 impregnation Methods 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 238000012546 transfer Methods 0.000 description 8
- 231100000614 poison Toxicity 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000007872 degassing Methods 0.000 description 6
- 230000006870 function Effects 0.000 description 6
- 239000002574 poison Substances 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- ZQDPJFUHLCOCRG-UHFFFAOYSA-N 3-hexene Chemical compound CCC=CCC ZQDPJFUHLCOCRG-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000004231 fluid catalytic cracking Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910001038 basic metal oxide Inorganic materials 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000011143 downstream manufacturing Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 238000005382 thermal cycling Methods 0.000 description 2
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 description 1
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000000556 agonist Substances 0.000 description 1
- 230000001270 agonistic effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- IZNOACPNJFLSAF-UHFFFAOYSA-N but-2-ene;prop-1-ene Chemical compound CC=C.CC=CC IZNOACPNJFLSAF-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 210000003278 egg shell Anatomy 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 210000000540 fraction c Anatomy 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- WZHKDGJSXCTSCK-UHFFFAOYSA-N hept-3-ene Chemical compound CCCC=CCC WZHKDGJSXCTSCK-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000005872 self-metathesis reaction Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/23—Rearrangement of carbon-to-carbon unsaturated bonds
- C07C5/25—Migration of carbon-to-carbon double bonds
- C07C5/2506—Catalytic processes
- C07C5/2512—Catalytic processes with metal oxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/23—Rearrangement of carbon-to-carbon unsaturated bonds
- C07C5/25—Migration of carbon-to-carbon double bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/14—Silica and magnesia
-
- B01J35/40—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/08—Alkenes with four carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
- C07C4/10—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from acyclic hydrocarbons
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Description
文中揭示之實施例一般而言係有關於得自主要用於經由複分解而使C4烯烴轉化成丙烯烴之裂解方法(諸如蒸氣或流體催化裂解)之C3至C6烴餾份的加工。更特定地，文中揭示之實施例係有關於用於乙烯烴及2-丁烯之複分解及/或根據平衡作用使1-丁烯轉化成2-丁烯之異構化作用或2-丁烯轉化成1-丁烯之異構化作用的催化劑。The embodiments disclosed herein have generally based on C primarily for conversion from propan-olefin cracking process (such as steam or fluid catalytic cracking) by the metathesis of C 4 olefins of 3 to C 6 hydrocarbon fraction processing embodiment. More specifically, the examples disclosed herein relate to the metathesis of ethylene and 2-butene and/or the isomerization of 1-butene to 2-butene or 2-butene according to equilibrium A catalyst that is converted to isomerization of 1-butene.
在，諸如美國專利第7,223,895號中所闡明之典型烯烴工廠中，先後有用於移除甲烷及氫之輕餾份(front-end)去甲烷塔、及用於移除乙烷、乙烯及C2乙炔之去乙烷塔。得自本去乙烷塔之塔底產物係由碳數範圍自C3至C6之化合物的混合物組成。典型上本混合物可藉分餾而分離成不同碳數化合物。In a typical olefins plant as set forth in U.S. Patent No. 7,223,895, there is a front-end demethanizer for the removal of methane and hydrogen, and for the removal of ethane, ethylene and C 2 . Deacetylation tower of acetylene. The product obtained from the present system to deethanizer bottoms of the carbon number range from the mixture of compounds of C 3 to C 6 components. Typically, the mixture can be separated into different carbon number compounds by fractional distillation.
移除呈產物形式之該C3餾份(主要為丙烯)且其最後係用於製備聚丙烯或用於，諸如環氧丙烷、異丙苯或丙烯腈之化學合成。必須藉分餾或氫化而移除甲基乙炔及丙二烯(MAPD)雜質。較佳進行氫化反應，因為這些高不飽和性C3化合物最後會形成丙烯，藉以增加產率。The product was removed in the form of the C 3 fraction (mainly propylene) and its last line for the preparation of polypropylene or for chemical synthesis such as propylene oxide, cumene, or acrylonitrile of. Methyl acetylene and propadiene (MAPD) impurities must be removed by fractional distillation or hydrogenation. The hydrogenation reaction is preferably conducted because of these highly unsaturated C 3 compounds end up forming a propylene, so as to increase yield.
可以使用許多方法處理由C4乙炔、丁二烯、異-及正丁烯、以及異-及正丁烷所組成之C4餾份。典型的蒸氣裂解器C4餾份含有以重量%表示之以下組份：Many methods may be used by the processing C 4 acetylenes, butadiene, iso - C and n-butane fraction consisting of 4 - and n-butene, and isobutyl. A typical steam cracker C 4 fraction comprises the following components expressed in weight% of:
典型上，首先移除丁二烯及C4乙炔。該移除步驟可藉氫化或萃取而完成。若使用萃取，殘留的1-丁烯及2-丁烯基本上仍然維持與該最初進料之1-丁烯及2-丁烯相同的比率。若使用氫化，得自丁二烯氫化反應之初產物為1-丁烯。其後，在相同反應系統內發生氫異構化反應，因此將該1-丁烯轉變成2-丁烯。本反應之程度取決於該氫化系統內之催化劑及反應條件。然而，通常的做法是限制該氫異構化程度以避免“過度氫化”及自丁烯產生丁烷。就下游操作而言，其代表丁烯進料之損失。殘留在該混合物內之丁烯由正烯烴(1-丁烯、2-丁烯)及異-烯烴(異丁烯)組成。該混合物內之C4餾份由得自原有原料及在該等氫化步驟內所製成的異-及正-丁烷以及任何少量之未經轉化或未經回收的丁二烯所組成。Typically the first removed butadiene, acetylene, and C 4. This removal step can be accomplished by hydrogenation or extraction. If extraction is used, the residual 1-butene and 2-butene remain substantially the same ratio as the 1-butene and 2-butene initially fed. If hydrogenation is used, the initial product from the butadiene hydrogenation reaction is 1-butene. Thereafter, a hydroisomerization reaction takes place in the same reaction system, so the 1-butene is converted into 2-butene. The extent of this reaction depends on the catalyst and reaction conditions within the hydrogenation system. However, it is common practice to limit the degree of hydrogen isomerization to avoid "over-hydrogenation" and the production of butane from butene. For downstream operations, it represents the loss of butene feed. The butene remaining in the mixture consists of a normal olefin (1-butene, 2-butene) and an iso-olefin (isobutylene). The C4 fraction in the mixture consists of the starting materials and the iso- and n-butanes produced in the hydrogenation steps, as well as any minor amounts of unconverted or unrecovered butadiene.
該等丁烯具有許多用途，且在許多方法中，在一特定分子內較佳進行雙鍵之異構化反應。雙鍵異構化反應為在不會改變一分子的結構下，在該分子內之雙鍵位置的移動。其不同於其中結構會改變(最典型代表異構形式與正形式間之互換)之架構異構化反應。架構異構化反應係藉完全不同於雙鍵異構化反應之機制而進行。典型上使用經促效之酸性催化劑以進行架構異構化反應。These butenes have many uses, and in many processes, isomerization of double bonds is preferred in a particular molecule. The double bond isomerization reaction is a shift in the position of a double bond within the molecule without changing the structure of one molecule. It differs from the structural isomerization reaction in which the structure changes (most typically represents the exchange between the isomeric form and the positive form). The structural isomerization reaction is carried out by a mechanism that is completely different from the double bond isomerization reaction. An agonistic acidic catalyst is typically employed to carry out the framework isomerization reaction.
雙鍵異構化反應為一種受平衡限制之反應。就1-丁烯與2-丁烯(順式及反式)間之平衡而言，於較低溫度下，有利於丙烯烴(2-丁烯)。以純丁烯-1-或純丁烯-1或其等之混合物開始，該反應會朝丁烯-2至丁烯-1的平衡比移動。有兩主要反應路線。其中之一者為其中該反應典型上係於較低溫度在氫存在下，在貴重金屬催化劑上進行，而另一者為其中該反應通常於較高溫度下在鹼性金屬氧化物催化劑上進行且未使用氫的非氫異構化反應。The double bond isomerization reaction is a reaction that is limited by equilibrium. In the case of a balance between 1-butene and 2-butene (cis and trans), propylene (2-butene) is favored at a lower temperature. Starting with pure butene-1- or pure butene-1 or a mixture thereof, the reaction will shift towards the equilibrium ratio of butene-2 to butene-1. There are two main reaction routes. One of them is wherein the reaction is typically carried out on a precious metal catalyst in the presence of hydrogen at a lower temperature, while the other is where the reaction is usually carried out on a basic metal oxide catalyst at a higher temperature. And no non-hydroisomerization reaction of hydrogen is used.
雙鍵氫異構化反應可在氫化反應器內進行。該氫異構化反應使用貴重金屬催化劑(諸如Pt或Pd)載少量氫且於一般溫度下進行，而後者不使用氫且典型上於較高溫度下使用鹼性金屬氧化物催化劑。通常於一般溫度下進行雙鍵氫異構化反應以使該內烯烴(例如不同於1-丁烯之2-丁烯)增至最多，因為於較低溫度下，熱力學平衡有利於該內烯烴。就下游製程而言，當有需要製造內烯烴時，本技術通常較佳。使2-丁烯進行加乙烯分解反應以製造丙烯的方法為此種反應。該加乙烯分解反應(複分解)為2-丁烯+乙烯→兩個丙烯。典型上使用混合型正丁烯(1-及2-丁烯)作為用於複分解反應之進料且該複分解反應之上游係使用氫異構化反應以使進料中之2-丁烯增至最大。The double bond hydroisomerization reaction can be carried out in a hydrogenation reactor. The hydroisomerization reaction uses a precious metal catalyst (such as Pt or Pd) to carry a small amount of hydrogen and is carried out at a normal temperature, while the latter does not use hydrogen and typically uses a basic metal oxide catalyst at a higher temperature. The double bond hydroisomerization reaction is usually carried out at a normal temperature to maximize the internal olefin (e.g., 2-butene different from 1-butene) because at a lower temperature, the thermodynamic equilibrium favors the internal olefin . In the case of downstream processes, the art is generally preferred when it is desired to produce internal olefins. A method in which 2-butene is subjected to an ethylene decomposition reaction to produce propylene is such a reaction. The ethylene decomposition reaction (metathesis) is 2-butene + ethylene → two propylene. Mixed n-butene (1- and 2-butene) is typically used as the feed for the metathesis reaction and the upstream of the metathesis reaction uses a hydroisomerization reaction to increase the 2-butene in the feed to maximum.
然而，亦可不需要在獨立異構化反應器內使用氫或併用複分解的情況下獨立進行雙鍵異構化反應且典型上於較高溫度下使用鹼金屬氧化物催化劑。雖然內烯烴仍然是該混合物內之主要正丁烯，但是由於溫度增加，該藉平衡而形成之α烯烴(1-丁烯)亦會增加。在氫不存在下使用該鹼金屬氧化物催化劑可排除起因於氫異構化系統之藉氫化反應而產生烷烴之作用。However, it is also possible to carry out the double bond isomerization reaction independently without using hydrogen or in the case of metathesis in an independent isomerization reactor and typically using an alkali metal oxide catalyst at a higher temperature. Although the internal olefin is still the main n-butene in the mixture, the alpha olefin (1-butene) formed by the equilibrium also increases due to an increase in temperature. The use of the alkali metal oxide catalyst in the absence of hydrogen eliminates the action of alkane generation resulting from the hydrogenation reaction of the hydrogen isomerization system.
2-丁烯之加乙烯分解反應(複分解)係於高溫(例如300℃)下在複分解催化劑上進行。然而，在本複分解反應中僅2-丁烯沈澱。1-丁烯與乙烯之複分解反應被認為是一種非生產性反應，因為本複分解反應之產物基本上與該等反應物相同。因此，最好同時在複分解期間盡量將該1-丁烯轉化成2-丁烯以因此使丙烯之產生增至最大。在這些條件下，係使用非氫異構化反應且典型上使該鹼金屬氧化物異構化反應催化劑與複分解催化劑物理性混合以同時進行這兩種反應。The ethylene decomposition reaction (metathesis) of 2-butene is carried out on a metathesis catalyst at a high temperature (for example, 300 ° C). However, only 2-butene precipitated in the present metathesis reaction. The metathesis reaction of 1-butene with ethylene is considered to be a non-productive reaction because the products of the metathesis reaction are substantially identical to the reactants. Therefore, it is preferred to convert the 1-butene to 2-butene as much as possible during metathesis to thereby maximize the production of propylene. Under these conditions, a non-hydroisomerization reaction is used and the alkali metal oxide isomerization catalyst is typically physically mixed with a metathesis catalyst to carry out both reactions simultaneously.
習知具有異構化反應之複分解包括如上述使混合型正丁烯(1-丁烯及2-丁烯)與乙烯反應以產生丙烯。這些反應係在第VIA或VIIA族金屬氧化物複分解催化劑(其係與鹼金屬氧化物異構化反應催化劑一起經承載或未經承載)存在下進行。用於複分解之典型催化劑為承載於氧化矽上之氧化鎢或承載於氧化鋁上之氧化錸。適於烯烴之複分解的催化劑實例描述在，例如美國專利第6,683,019號中。It is known that metathesis having an isomerization reaction involves reacting mixed n-butene (1-butene and 2-butene) with ethylene to produce propylene as described above. These reactions are carried out in the presence of a Group VIA or VIIA metal oxide metathesis catalyst which is supported or unsupported with an alkali metal oxide isomerization catalyst. Typical catalysts for metathesis are tungsten oxide supported on cerium oxide or cerium oxide supported on alumina. Examples of catalysts suitable for the metathesis of olefins are described, for example, in U.S. Patent No. 6,683,019.
然而，通常在該複分解反應器內使用雙鍵異構化反應催化劑以使1-丁烯轉化成2-丁烯並持續進行反應。典型的雙鍵異構化反應催化劑包括經承載或未經承載之鹼金屬氧化物(第IIA族)。氫異構化反應特別不佳，因為於該反應之高溫下，所需要的氫會使該等烯烴反應物之部份餾份飽和而轉化成烷烴，因此減少該產物之產率。例如美國專利第6,875,901號揭示一種使用鹼金屬氧化物催化劑(諸如高純度氧化鎂催化劑，其可以呈粉末、小粒、擠出物等形式)使烯烴進行異構化反應的方法。氧化鎂及氧化鈣為可以與該複分解催化劑物理性混合的此等雙鍵異構化反應催化劑之實例。就異丁烯轉化成正丁烯之架構異構化反應而言，並不存在等效之輔催化劑。就兼使用複分解催化劑及共混合型雙鍵異構化反應催化劑之習知複分解系統而言，必須將丁二烯移除至小於500ppm之含量以避免該雙鍵異構化反應催化劑之快速堵塞。該複分解催化劑本身可耐受至高10,000ppm之丁二烯含量。However, a double bond isomerization catalyst is typically employed in the metathesis reactor to convert 1-butene to 2-butene and to continue the reaction. Typical double bond isomerization catalysts include supported or unsupported alkali metal oxides (Group IIA). The hydroisomerization reaction is particularly poor because at the elevated temperatures of the reaction, the hydrogen required will saturate a portion of the olefin reactant to convert it to an alkane, thereby reducing the yield of the product. For example, U.S. Patent No. 6,875,901 discloses a process for the isomerization of an olefin using an alkali metal oxide catalyst such as a high purity magnesium oxide catalyst which may be in the form of a powder, granules, extrudates or the like. Magnesium oxide and calcium oxide are examples of such double bond isomerization catalysts which can be physically mixed with the metathesis catalyst. In the case of the structural isomerization reaction in which isobutylene is converted to n-butene, there is no equivalent cocatalyst. For a conventional metathesis system that uses both a metathesis catalyst and a co-mixed double bond isomerization catalyst, the butadiene must be removed to a level of less than 500 ppm to avoid rapid clogging of the double bond isomerization catalyst. The metathesis catalyst itself can withstand a butadiene content of up to 10,000 ppm.
在該複分解反應步驟進行前，典型上自該進料移除異丁烯。該異丁烯與乙烯之反應不具生產性且在過量乙烯存在下，複分解反應本身及/或其它C4化合物會受到限制。不具生產性的反應基本上會佔有催化劑部位但不產生產物。若使其仍維持在送至複分解單元之進料內，本非反應性物種之濃度會增加，因此造成容量的限制。對於異丁烯移除之取捨包括使其與甲醇反應以產生甲基第三丁基醚(MTBE)或藉分餾而自該等丁烯移除異丁烯。美國專利第6,358,482號揭示在複分解進行前，自C4混合物移除異丁烯。本方案進一步在美國專利第6,075,173及第5,898,091號中有表示。美國專利第6,580,009號揭示一種用於自有限的乙烯餾份製造丙烯及己烯的方法。就自0.05至0.60之乙烯對丁烯(以正-丁烯表示)的莫耳比而言，係使用萃剩物(raffinate)II物料流作為該C4進料。萃剩物II物料流之定義為異丁烯移除後之物料流。如美國專利第5,087,780所述，亦可藉使用合併式催化蒸餾氫異構化反應去異丁烯塔系統將該1-丁烯異構化以形成2-丁烯而以高效率移除該異丁烯並兼回收正-丁烯來完成異丁烯自該C4物料流之移除。Isobutylene is typically removed from the feed prior to the metathesis reaction step. The reaction of isobutylene with ethylene non-productive and in the presence of excess ethylene, the metathesis reaction itself and / or other C 4 compounds is limited. An unproductive reaction will essentially occupy the catalyst site but will not produce a product. If it is still maintained in the feed to the metathesis unit, the concentration of the non-reactive species will increase, thus causing a limitation in capacity. The trade-off for isobutene includes reacting it with methanol to produce methyl tertiary butyl ether (MTBE) or by fractional distillation to remove isobutylene from the butenes. U.S. Patent No. 6,358,482 discloses prior to metathesis to occur, removing isobutylene from C 4 mixtures. The present invention is further described in U.S. Patent Nos. 6,075,173 and 5,898,091. U.S. Patent No. 6,580,009 discloses a process for the manufacture of propylene and hexene from a limited ethylene fraction. From 0.05 to 0.60 on the ethylene to butene (in n - butene shown) in terms of molar ratio, based extraction using the remaining product (raffinate) II stream as the C 4 feedstock. The Residue II stream is defined as the stream after isobutylene removal. As described in U.S. Patent No. 5,087,780, the 1-butene can be isomerized to form 2-butene by a combined catalytic distillation hydrogen isomerization reaction to the isobutylene column system to remove the isobutene with high efficiency and recovering n - butene from isobutene to complete removal of the C 4 stream.
高溫雙鍵異構化反應催化劑亦可單獨用於雙鍵異構化反應，但是在複分解催化劑及/或乙烯存在下不能使用。例如1-丁烯為用於製造某些等級之聚乙烯的貴重共單體。如USP 6,875,901中所述，可經由2-丁烯之異構化反應並配合分餾而製成1-丁烯。而且如USP 6,727,396中所述，此種異構化反應催化劑可用於使內己烯異構物(2-及3-己烯)轉化成1-己烯之異構化反應。1-己烯亦為用於聚乙烯之貴重共單體。在本情況下，該複分解係在1-丁烯與其本身(1-丁烯+1-丁烯→乙烯+3-己烯)之間進行。本反應使用如上文所述之類似複分解催化劑，但精確地說，送至該複分解步驟之進料必須是高濃度1-丁烯。如USP 6,875,901所述，使用該鹼金屬氧化物異構化反應催化劑以產生高濃度1-丁烯之物料流。特定地使該1-丁烯僅進行複分解以避免在該步驟內發生異構化功能。然後使所形成3-己烯接受一各別的高溫(非氫異構化雙鍵異構化步驟)。此異構化反應之優點為就該α烯烴而言，於較高溫度下可獲得有利的平衡且不存在將烯烴氫化成烷烴之氫。The high temperature double bond isomerization catalyst can also be used alone for the double bond isomerization reaction, but cannot be used in the presence of a metathesis catalyst and/or ethylene. For example, 1-butene is a valuable comonomer used to make certain grades of polyethylene. 1-butene can be prepared by isomerization of 2-butene and by fractional distillation as described in USP 6,875,901. Moreover, such an isomerization catalyst can be used to convert the internal hexene isomer (2- and 3-hexene) to the isomerization reaction of 1-hexene as described in USP 6,727,396. 1-hexene is also a valuable comonomer for polyethylene. In the present case, the metathesis is carried out between 1-butene and itself (1-butene+1-butene→ethylene+3-hexene). The reaction uses a similar metathesis catalyst as described above, but to be precise, the feed to the metathesis step must be a high concentration of 1-butene. The alkali metal oxide isomerization catalyst is used to produce a high concentration 1-butene stream as described in USP 6,875,901. The 1-butene is specifically subjected to metathesis only to avoid the isomerization function occurring in this step. The resulting 3-hexene is then subjected to a separate high temperature (nonhydroisomerization double bond isomerization step). An advantage of this isomerization reaction is that in the case of the alpha olefin, a favorable equilibrium can be obtained at higher temperatures and there is no hydrogen which hydrogenates the olefin to an alkane.
該等複分解催化劑及雙鍵異構化反應催化劑對毒物很敏感。毒物包括水、CO2、含氧化合物(諸如MTBE)、硫化合物、氮化合物、及重金屬。通常的做法是使用該複分解反應系統之上游保護床以確保這些毒物之移除。只要該等毒物經移除且其後不導入新的毒物，這些保護床是否直接設置在該複分解反應系統之前或另外在上游並不重要。典型的保護床吸附劑為氧化鋁及/或活化氧化鋁。亦可使用鹼金屬氧化物(諸如氧化鎂及/或氧化鈣)以作為保護床材料。於低溫下，其等可吸附水並與含氧化合物(諸如甲醇)反應以形成水及二氧化碳。其後藉其它鹼氧化物部位而吸附所形成水。The metathesis catalysts and double bond isomerization catalysts are very sensitive to poisons. Toxic substances include water, CO 2 , oxygenates (such as MTBE), sulfur compounds, nitrogen compounds, and heavy metals. It is common practice to use an upstream guard bed of the metathesis reaction system to ensure removal of these poisons. It is not important whether these guard beds are placed directly before the metathesis reaction system or otherwise upstream as long as the poisons are removed and no new poisons are introduced thereafter. Typical guard bed adsorbents are alumina and/or activated alumina. Alkali metal oxides such as magnesium oxide and/or calcium oxide can also be used as the guard bed material. At low temperatures, they can adsorb water and react with oxygenates such as methanol to form water and carbon dioxide. Thereafter, the formed water is adsorbed by other alkali oxide sites.
複分解反應對該烯烴雙鍵之位置及各該分子之立體結構很敏感。一對烯烴可吸附至該表面上並與該等雙鍵之各側上之碳基交換雙鍵位置。複分解反應可被分類為具生產性、半生產性或非生產性。如上述，非生產性反應會導致基本上不發生反應。當該等雙鍵經複分解反應轉移時，新的分子與原來吸附之分子相同，因此未發生生產性反應。其係為對稱烯烴間之反應或乙烯與α烯烴間之反應所特有。若發生完全生產性反應，則不管該等分子佔有之位置的定向如何，皆會產生新產物。可形成兩丙烯分子之乙烯與2-丁烯間所進行的反應為完全生產性反應。半生產性反應係在立體上受遮蔽。若該等烯烴對以一定向吸附，則當雙鍵轉移時，會形成新產物。或者，若其等以不同的立體構型吸附，則當該等雙鍵轉移時，會形成相同烯烴，因此未形成新產物。於不同速率(完全生產性反應通常比半生產性反應還快速)下且對丙烯使用不同重量選擇率以進行各種複分解反應。表2摘述乙烯與各種丁烯間之反應、及丁烯本身之間的反應。The metathesis reaction is sensitive to the position of the olefinic double bond and the steric structure of each of the molecules. A pair of olefins can be adsorbed onto the surface and exchanged for a double bond position with the carbon groups on each side of the double bonds. Metathesis reactions can be classified as productive, semi-productive or non-productive. As described above, the non-productive reaction results in substantially no reaction. When the double bonds are transferred by the metathesis reaction, the new molecules are identical to the originally adsorbed molecules, so that no productive reaction occurs. It is unique to the reaction between symmetric olefins or the reaction between ethylene and alpha olefins. In the event of a complete productive reaction, a new product will be produced regardless of the orientation of the position occupied by the molecules. The reaction between ethylene and 2-butene, which can form two propylene molecules, is a fully productive reaction. Semi-productive reactions are obscured in three dimensions. If the olefins are adsorbed in a certain direction, a new product is formed when the double bond is transferred. Alternatively, if they are adsorbed in different stereo configurations, when the double bonds are transferred, the same olefin is formed, so that no new product is formed. Different metathesis reactions are carried out at different rates (completely productive reactions are generally faster than semi-productive reactions) and different weight options are used for propylene to carry out various metathesis reactions. Table 2 summarizes the reaction between ethylene and various butenes and the reaction between butene itself.
所列示反應代表使用乙烯之基礎反應(反應1、4及5)以及各種C4烯烴間之反應。尤其重要的是區分涉及該反應之對丙烯與對總C4烯烴(其包括異丁烯)之選擇率、及對丙烯與對正C4烯烴之選擇率。異丁烯與2-丁烯之反應6)可產生丙烯及分支鏈C5分子。就本反應而言，係自總C4烯烴以37.5重量%選擇率產生丙烯(與反應2類似)，但是自正C4烯烴(2-丁烯)以75重量%選擇率產生丙烯。就定義而言，習知複分解之定義為該C4烯烴物料流與乙烯之反應。然而，亦可在作為進料之乙烯的不存在下，使該C4物料流進行反應。本反應被稱為自動或自複分解。在本情況下，反應2、3、6、及7為唯一可能的反應且在取決於該進料組成之速率下進行。The reactions listed represent the basic reaction using ethylene (Reactions 1, 4 and 5) and the reaction between various C 4 olefins. It is particularly important to differentiate the selectivity of the reaction of propylene with total C 4 olefins (including isobutylene), the propylene and the selectivity of n-C 4 olefins. The reaction of isobutylene with 2-butene 6) produces propylene and branched C 5 molecules. For purposes of this reaction, based the total C 4 olefins from 37.5 wt% selectivity to produce propylene (similar to reaction 2), but since the n-C 4 olefins (2-butene) produced in a 75 wt% propylene selectivity. By definition, conventional definitions for the metathesis of C 4 olefin stream with ethylene to react. However, the C 4 stream can also be reacted in the absence of ethylene as a feed. This reaction is called automatic or self-metathesis. In the present case, reactions 2, 3, 6, and 7 are the only possible reactions and are carried out at a rate that depends on the composition of the feed.
在用於製備丙烯之習知複分解中，注意力集中於使可產生丙烯之反應1增至最大。其可以使對丙烯之選擇率增至最大。因此，使用過量乙烯以減少丁烯與其本身之反應(反應2、3、6、及7)程度。乙烯對正-丁烯之理論比為1/1莫耳比或0.5重量比，但是在習知複分解中通常使用明顯較高的比率(典型上，1.3或更大莫耳比)以使反應2、3、6及7減至最低。在過量乙烯的條件下，且基於異丁烯與1-丁烯皆不會與乙烯反應(見反應4及5)之事實，係使用雙製程順序。第一，在複分解進行前移除該異丁烯。若未移除異丁烯，由於該等正-丁烯經再循，其可積增以獲得高產率。第二，藉包括一雙鍵異構化反應催化劑(諸如經該複分解催化劑摻合之氧化鎂)而將1-丁烯異構化以轉化成2-丁烯。應注意的是本催化劑不會導致架構異構化反應(異丁烯轉化成正丁烯)，但僅將雙鍵自第1位置轉移至第2位置。因此，藉使用過量乙烯操作，在反應前可自該複分解進料消除異丁烯，且使利用雙鍵異構化反應催化劑之反應1增至最大。In the conventional metathesis for the preparation of propylene, attention has been focused on increasing the reaction 1 which produces propylene to the maximum. It can maximize the selectivity to propylene. Therefore, excess ethylene is used to reduce the extent of the reaction of butene with itself (reactions 2, 3, 6, and 7). The theoretical ratio of ethylene to n-butene is 1/1 molar ratio or 0.5 weight ratio, but in conventional metathesis a significantly higher ratio (typically 1.3 or greater molar ratio) is usually used to make the reaction 2 , 3, 6 and 7 are reduced to a minimum. In the case of excess ethylene, and based on the fact that neither isobutylene nor 1-butene reacts with ethylene (see reactions 4 and 5), a dual process sequence is used. First, the isobutylene is removed prior to metathesis. If isobutene is not removed, it can be accumulated to obtain a high yield since the n-butene is recycled. Second, 1-butene is isomerized to convert to 2-butene by including a double bond isomerization catalyst such as magnesium oxide blended with the metathesis catalyst. It should be noted that this catalyst does not cause a structural isomerization reaction (isobutylene is converted to n-butene), but only the double bond is transferred from the first position to the second position. Thus, by using an excess of ethylene, the isobutene can be eliminated from the metathesis feed prior to the reaction and the reaction 1 using the double bond isomerization catalyst is maximized.
如上述，氧化鎂催化劑可以與複分解催化劑混合以在相同反應器內兼進行雙鍵異構化反應及複分解。在此種系統內，該氧化鎂有兩種功用。第一，該氧化鎂可作為保護床，其可吸附各種含氧化合物及水以保護該複分解催化劑。於該複分解之較高溫度下，吸附能力比於更接近環境之溫度下低很多，但是本功用在經由如上述之保護床而移除大塊毒物後可提供重要的第二毒物吸附步驟。第二，如上述，乙烯及1-丁烯之反應不具生產性；因為1-丁烯基本上不會與乙烯反應，所以1-丁烯會積增在該再系統物料流內。為了避免1-丁烯積增，可使用雙鍵異構化反應催化劑(諸如氧化鎂)以將該1-丁烯異構化以產生2-丁烯，因為在該反應進行期間，該2-丁烯會耗盡。As described above, the magnesium oxide catalyst can be mixed with the metathesis catalyst to carry out the double bond isomerization reaction and metathesis in the same reactor. In such a system, the magnesium oxide has two functions. First, the magnesium oxide acts as a guard bed that adsorbs various oxygenates and water to protect the metathesis catalyst. At the higher temperatures of the metathesis, the adsorption capacity is much lower than at temperatures closer to the environment, but this function provides an important second poison adsorption step after removal of bulk poisons via a guard bed as described above. Second, as described above, the reaction of ethylene and 1-butene is not productive; since 1-butene does not substantially react with ethylene, 1-butene is accumulated in the re-system stream. In order to avoid 1-butene accumulation, a double bond isomerization catalyst such as magnesium oxide may be used to isomerize the 1-butene to produce 2-butene because during the reaction, the 2- Butene will be depleted.
雙鍵異構化反應催化劑(諸如氧化鎂)目前在市面上係以具有約5毫米之有效直徑的錠劑形式使用。如文中使用，有效直徑係指若經模製成球狀物時，非球形顆粒可具有之直徑。當僅處理丁烯時，這些錠劑具有良好異構化活性。然而，這些錠劑在乙烯存在下，僅具有適於使1-丁烯進行異構化反應以產生2-丁烯，費時短時間的活性。此外，隨著反應循環數增加，其等之效能逐漸惡化。經數次再生/反應循環後，其等之異構化活性變低。本效能不足會導致經過一段時間後1-丁烯在該系統內快速積增，因此會藉液壓性限制該再循環而限制反應器效能，且限制可合乎經濟地獲得之丁烯轉化成丙烯之總轉化率。當操作這些作為僅用於自該內烯烴製備終端烯烴之雙鍵異構化反應催化劑的催化劑時，會經歷類似的活性損失。Double bond isomerization catalysts, such as magnesium oxide, are currently commercially available in the form of tablets having an effective diameter of about 5 mm. As used herein, an effective diameter means that the non-spherical particles may have a diameter if molded into a sphere. These tablets have good isomerization activity when only butene is treated. However, these tablets have only an activity suitable for the isomerization of 1-butene to produce 2-butene in the presence of ethylene, which takes a short time. In addition, as the number of reaction cycles increases, the efficiency of the processes gradually deteriorates. After several regeneration/reaction cycles, the isomerization activity of the catalysts becomes lower. This lack of performance results in a rapid accumulation of 1-butene in the system over time, thus limiting the reactor efficiency by hydraulically limiting the recycle and limiting the economically available conversion of butene to propylene. Total conversion rate. When operating these catalysts as catalysts for the double bond isomerization reaction only for the preparation of terminal olefins from the internal olefin, similar loss of activity is experienced.
本工業中已熟知較小尺寸之催化劑顆粒在該等反應循環期間具有更佳效能。其原因為內質量轉移抗性減少。其可以使該等反應物更能接近催化劑部位。藉減少質量轉移抗性，可獲得改良的反應性。然而，並未改善隨著再生循環而導致的活性損失之問題。由於再生所導致的活性損失並非起因於以有效直徑為變數之簡單質量轉移限制，而係起因於藉，例如焦碳移除所需之較高溫度而產生之燒結所導致的催化劑顆粒(具任何尺寸)表面積之損失。Smaller sized catalyst particles are well known in the art to have better performance during such reaction cycles. The reason is that the internal mass transfer resistance is reduced. It can make the reactants more accessible to the catalyst site. Improved reactivity can be obtained by reducing mass transfer resistance. However, the problem of loss of activity with the regeneration cycle has not been improved. The loss of activity due to regeneration is not due to simple mass transfer limitations with effective diameter as a function of catalyst particles due to sintering resulting from higher temperatures required for coke removal, such as coke removal (with any Size) loss of surface area.
已進行某些嘗試以改良氧化鎂催化劑的效能。例如美國專利第6,875,901號揭示藉限制某些雜質(諸如磷、硫、過渡金屬等)而改良氧化鎂異構化反應催化劑之去活化速率的方法，然而在乙烯存在下之去活化作用仍然成為問題。Some attempts have been made to improve the performance of magnesium oxide catalysts. For example, U.S. Patent No. 6,875,901 discloses a method for improving the deactivation rate of a magnesium oxide isomerization catalyst by limiting certain impurities such as phosphorus, sulfur, transition metals, etc., however deactivation in the presence of ethylene remains a problem. .
如上述，仍有需要可改良該複分解方法之總效能、增加丙烯產率及減少1-丁烯再循環滌洗之鹼金屬氧化物雙鍵異構化反應催化劑。亦有需要用於使內烯烴轉化成末端烯烴(例如2-丁烯轉化成1-丁烯、或2-己烯或3-己烯轉化成1-己烯)之該簡單雙鍵異構化反應之這些催化劑的改良物。就這些系統而言，有需要減少該逐循環去活化作用，因此可在該完全催化劑生命週期內維持較高活性。As described above, there is still a need for a catalyst for improving the overall efficiency of the metathesis process, increasing the yield of propylene, and reducing the double bond isomerization reaction of the 1-butene recycle scrub. There is also a need for such simple double bond isomerization for the conversion of internal olefins to terminal olefins such as 2-butene to 1-butene or 2-hexene or 3-hexene to 1-hexene. A modification of these catalysts that react. For these systems, there is a need to reduce this cycle-by-cycle deactivation so that higher activity can be maintained over the full catalyst life cycle.
在一方面，文中揭示之實施例係有關於用於烯烴之雙鍵異構化反應的方法，該方法包括：使用包括一含結構安定劑之活化鹼金屬氧化物異構化反應催化劑的固定床接觸含烯烴之流體物料流以將該烯烴之至少一部份轉化成其異構物。In one aspect, the embodiments disclosed herein relate to a process for the double bond isomerization of olefins comprising: using a fixed bed comprising an activated alkali metal oxide isomerization catalyst comprising a structural stabilizer Contacting an olefin-containing fluid stream to convert at least a portion of the olefin to its isomer.
在另一方面中，文中揭示之實施例係有關於用於烯烴之雙鍵異構化反應的方法，該方法包括：使用包括一具有在0.25毫米至4.0毫米範圍內之有效直徑之活化鹼金屬氧化物異構反應催化劑的固定床接觸含烯烴之流體物料流以將該烯烴之至少一部份轉化成其異構物。In another aspect, the embodiments disclosed herein relate to a method for the double bond isomerization reaction of an olefin, the method comprising: using an activated alkali metal comprising an effective diameter in the range of 0.25 mm to 4.0 mm The fixed bed of the oxide isomerization catalyst is contacted with an olefin-containing fluid stream to convert at least a portion of the olefin to its isomer.
在另一方面中，文中揭示之實施例係有關於用於製備丙烯之方法，其包括：將含正-丁烯、異丁烯、及烷烴之烴物料流分餾成包括含異丁烯之輕C4餾份及含正-丁烯與烷烴之重C4餾份的至少兩餾份；將乙烯及該重C4餾份饋至包括一複分解催化劑及一含結構安定劑之活化鹼金屬氧化物異構化反應催化劑的固定床反應器內，使用該活化鹼金屬氧化物異構化反應催化劑接觸重C4餾份以將該1-丁烯之至少一部份轉化成2-丁烯；並使用一複分解催化劑接觸乙烯及該2-丁烯之至少一部份以形成含丙烯、烯烴、任何未經反應之乙烯、及任何未經反應之1-丁烯及2-丁烯的複分解產物。In another aspect, the embodiments disclosed herein relates to a method for preparing a system of propylene, comprising: containing n - hydrocarbon-butene, isobutene, and the alkane stream comprising fractionated into isobutene-containing C 4 fraction of light And at least two fractions comprising a heavy C 4 fraction of n-butene and an alkane; feeding the ethylene and the heavy C 4 fraction to an isomerized alkali metal oxide isomerized comprising a metathesis catalyst and a structural stabilizer In the fixed bed reactor of the reaction catalyst, the activated alkali metal oxide isomerization catalyst is used to contact the heavy C 4 fraction to convert at least a portion of the 1-butene to 2-butene; and a metathesis is used. The catalyst is contacted with at least a portion of ethylene and the 2-butene to form a metathesis product comprising propylene, an olefin, any unreacted ethylene, and any unreacted 1-butene and 2-butene.
在另一方面中，文中揭示之實施例係有關於用於製備丙烯之方法，其包括：將含正-丁烯、異丁烯、及烷烴之烴物料流分餾成包括含異丁烯之輕C4餾份及含正-丁烯與烷烴之重C4餾份的至少兩餾份；將乙烯及該重C4餾份饋至含一複分解催化劑及活化鹼金屬氧化物異構化反應催化劑之固定床反應器，其中該異構化反應催化劑具有介於0.25與4.0毫米間之有效直徑且不含有安定劑；使用該活化鹼金屬氧化物異構化反應催化劑接觸該重C4餾份以將該1-丁烯之至少一部份轉化成2-丁烯；且使用一複分解催化劑接觸該乙烯及該2-丁烯之至少一部份以形成含丙烯、烷烴、任何未經反應的乙烯、及任何未經反應的1-丁烯及2-丁烯之複分解產物。In another aspect, the embodiments disclosed herein relates to a method for preparing a system of propylene, comprising: containing n - hydrocarbon-butene, isobutene, and the alkane stream comprising fractionated into isobutene-containing C 4 fraction of light And at least two fractions comprising a heavy C 4 fraction of n-butene and an alkane; feeding the ethylene and the heavy C 4 fraction to a fixed bed reaction comprising a metathesis catalyst and an activated alkali metal oxide isomerization catalyst Wherein the isomerization catalyst has an effective diameter between 0.25 and 4.0 mm and does not contain a stabilizer; the activated alkali metal oxide isomerization catalyst is used to contact the heavy C 4 fraction to Converting at least a portion of the butene to 2-butene; and contacting the ethylene and at least a portion of the 2-butene using a metathesis catalyst to form propylene, an alkane, any unreacted ethylene, and any The metathesis product of the reacted 1-butene and 2-butene.
自以下說明文及附加申請專利範圍可瞭解其它方面及優點。Other aspects and advantages will be apparent from the following description and the appended claims.
第1圖為以熱老化為變數，含結構安定劑之MgO錠劑之BET表面積之變化的圖示。Figure 1 is a graphical representation of the change in BET surface area of a MgO tablet containing a structural stabilizer as a function of heat aging.
第2A及2B圖為於650℃下經激烈的熱老化後，具不同尺寸之MgO錠劑之BET表面積及細孔結構的變化之圖示(2A=5毫米，2B=3毫米催化劑有效直徑)。Figures 2A and 2B are graphical representations of changes in BET surface area and pore structure of MgO tablets of different sizes after intense heat aging at 650 °C (2A = 5 mm, 2B = 3 mm effective diameter of catalyst) .
第3圖為根據文中揭示之實施例，使用催化劑進行異構化反應及複分解之方法的簡化製程流程圖。Figure 3 is a simplified process flow diagram of a method for isomerization and metathesis using a catalyst in accordance with an embodiment disclosed herein.
第4圖為與當在乙烯存在下使用典型氧化鎂催化劑比較，根據文中揭示之實施例，經過一段時間後，催化劑之催化劑活性的圖示。Figure 4 is a graphical representation of the catalyst activity of the catalyst over a period of time in accordance with the examples disclosed herein when compared to the use of a typical magnesium oxide catalyst in the presence of ethylene.
第5圖為在用於丙烯之複分解的最初及第5次循環中，不同程度之MgO顆粒之1-丁烯轉化率對累積老化的比較之圖示。Figure 5 is a graphical representation of the comparison of 1-butene conversion versus cumulative aging for varying degrees of MgO particles in the first and fifth cycles of metathesis of propylene.
在一方面中，文中揭示之實施例係有關於經由添加結構安定劑而改良經過多次再生之異構化反應催化劑的安定性之方法，在另一方面中，文中揭示之實施例係有關於不需添加安定劑，可藉減少異構化反應催化劑之有效直徑而改良經過多次再生之異構化反應催化劑之安定性的方法。In one aspect, the embodiments disclosed herein relate to a method for improving the stability of an isomerization catalyst that has undergone multiple regenerations via the addition of a structural stabilizer. In another aspect, the embodiments disclosed herein are related. The method of improving the stability of the isomerization catalyst which has been subjected to multiple regenerations can be improved by reducing the effective diameter of the isomerization catalyst without adding a stabilizer.
在另外的方面中，文中揭示之實施例一般而言係有關於得自裂解方法(諸如蒸氣或流體催化裂解)之C3至C6烴餾份的加工，其主要用於藉複分解而使C4烯烴轉化成丙烯。更特定地，文中揭示之實施例係有關於用於乙烯與2-丁烯之複分解及/或使內烯烴轉化成末端烯烴(例如2-丁烯轉化成1-丁烯)之異構化反應的催化劑。In a further aspect, the embodiments disclosed herein have generally based on C obtained from cleavage method (such as steam or fluid catalytic cracking) process the hydrocarbon fraction is 3 to C 6 embodiment, which is mainly used by the metathesis of C 4 olefins are converted to propylene. More specifically, the examples disclosed herein relate to isomerization reactions for the metathesis of ethylene with 2-butene and/or the conversion of internal olefins to terminal olefins (eg, 2-butene to 1-butene). Catalyst.
有用的異構化反應催化劑可包括鹼金屬氧化物，諸如可獨立或合併使用之氧化鎂、氧化鈣、氧化鋇、氧化鍶、及氧化鋰。可將其它氧化物(諸如氧化鈉或氧化鉀)併入該催化劑內以作為促效劑。在某些實施例中，用於異構化反應之該催化劑可以是氧化鎂(MgO)。雖然文中某些方面已根據氧化鎂加以描述，應該瞭解上述其它鹼金屬氧化物亦涵蓋在文中揭示之實施例的範圍內。Useful isomerization catalysts may include alkali metal oxides such as magnesium oxide, calcium oxide, cerium oxide, cerium oxide, and lithium oxide which may be used independently or in combination. Other oxides, such as sodium oxide or potassium oxide, can be incorporated into the catalyst to act as agonists. In certain embodiments, the catalyst used in the isomerization reaction can be magnesium oxide (MgO). Although certain aspects have been described in terms of magnesium oxide, it should be understood that other alkali metal oxides described above are also encompassed within the scope of the embodiments disclosed herein.
經熱循環處理(再生循環數)，氧化鎂雙鍵異構化反應催化劑會經歷老化變化。使用BET表面積及細孔大小測定法與粉末×射線繞射法(XRD)檢查各種MgO催化劑(就5毫米錠劑而言)之熱循環處理的影響。現有資料之分析顯示在多次再生循環處置下，該等MgO催化劑具有燒結作用(隨平均細孔直徑之漸增而損失表面積)。After thermal cycling (number of regeneration cycles), the magnesium oxide double bond isomerization catalyst undergoes aging changes. The effects of thermal cycling treatment of various MgO catalysts (for 5 mm tablets) were examined using BET surface area and pore size measurements and powder x-ray diffraction (XRD). Analysis of available data shows that the MgO catalysts have a sintering effect (the surface area is lost as the average pore diameter increases) under multiple regeneration cycles.
XRD資料亦表示隨著再生循環之漸增，主要MgO波峰變得更陡峭。其顯示根據使用德拜-謝樂(Debye-Scherer)方程式財波峰寬度測定值所獲得的平均微晶大小估測值，MgO之平均結晶狀大小隨多循環再生處置而增加。其結果表示多循環再生會導致晶體成長。晶體之成長會導致表面積的損失，因此該XRD資料證實該去活化作用。The XRD data also indicates that as the regeneration cycle increases, the main MgO peaks become steeper. It shows an estimate of the average crystallite size obtained from the measured value of the peak width of the Debye-Scherer equation, and the average crystal size of MgO increases with the multi-cycle regeneration treatment. The result indicates that multi-cycle regeneration leads to crystal growth. The growth of the crystal causes a loss of surface area, so the XRD data confirms the deactivation.
這些分析表示當該MgO催化劑進行多再生循環時，該BET表面積顯著減少，而平均微晶大小及平均細孔直徑相應地增加。在間歇再生下，經過多次循環，該等催化劑的物理上之變質會導致用於雙鍵異構化反應之該催化劑活性的去活化作用。由於該MgO催化劑之物理上的變質，所以發現逐漸縮短的循環長度。These analyses indicate that the BET surface area is significantly reduced as the MgO catalyst undergoes multiple regeneration cycles, while the average crystallite size and average pore diameter increase correspondingly. Under intermittent regeneration, the physical deterioration of the catalysts over several cycles leads to deactivation of the catalyst activity for the double bond isomerization reaction. Due to the physical deterioration of the MgO catalyst, a gradually shortened cycle length was found.
使用含30重量% SiO2(Ludox AS-30,Aldrich chemicals)在5毫米MgO錠劑(MGO)上之水性氧化矽黏合劑溶液，添加氧化矽以製備MGO-A及MGO-B。藉濕式浸漬法而製備試樣MGO-C及MGO-D。添加乾“照原樣(as is)”MgO小粒至含SiO2之水性溶液(就MGO-C而言，Ludox+蒸餾水、或就MGO-D而言，矽酸鈉+蒸餾水)。移除少量之過量液體後，於120℃下以烘箱乾燥該等濕小粒，費時24小時。MGO-A and MGO-B were prepared using an aqueous cerium oxide binder solution containing 30% by weight of SiO 2 (Ludox AS-30, Aldrich chemicals) on a 5 mm MgO tablet (MGO). Samples MGO-C and MGO-D were prepared by wet impregnation. Add dry "as is" MgO pellets to an aqueous solution containing SiO 2 (in the case of MGO-C, Ludox + distilled water, or in the case of MGO-D, sodium citrate + distilled water). After removing a small amount of excess liquid, the wet granules were dried in an oven at 120 ° C for 24 hours.
對該等經改質之MgO及標準MgO試樣進行多BET/細孔大小/細孔體積測定。在標準BET除氣方案(5℃加熱高至350℃，維持16小時)下，對該等經120℃烘箱乾燥之改質MgO試樣(MGO-A、MGO-B、MGO-C、及MGO-D)進行所有初BET測定。然後使用廢BET試樣以進行進一步的循環熱處置。各熱處置循環包括在不流動的空氣內以5℃/分鐘之速率急速上升至550℃下以進行12小時恆溫處置，接著冷却至120℃在不需要任何進一步除氣(“照原樣”經測定)下對所有經熱處置過之試樣進行BET測定。The multi-BET/pore size/pore volume measurement was performed on the modified MgO and standard MgO samples. Modified MgO samples (MGO-A, MGO-B, MGO-C, and MGO) dried in an oven at 120 ° C in a standard BET degassing scheme (5 ° C heating up to 350 ° C for 16 hours) -D) Perform all initial BET measurements. The spent BET sample is then used for further cyclic heat treatment. Each heat treatment cycle consists of a rapid rise to 5 ° C / min in a non-flowing air at a rate of 5 ° C / min for a 12 hour constant temperature treatment, followed by cooling to 120 ° C without any further degassing ("as is" BET measurements were performed on all heat treated samples.
如第1圖可知，就所有MgO試樣而言，表面積之最顯著損失發生在第一次循環，而後續暴露具有相當小的影響。與原有試樣比較，所有經處置試樣顯示明顯較高的表面積改良。試樣MGO-A、MGO-B及MGO-C顯示藉添加氧化矽可影響該表面積之安定性。As can be seen from Figure 1, for all MgO samples, the most significant loss of surface area occurs in the first cycle, while subsequent exposures have a relatively small effect. All treated samples showed significantly higher surface area improvements compared to the original samples. The samples MGO-A, MGO-B and MGO-C show that the addition of cerium oxide can affect the stability of the surface area.
MgO為具有FCC(面心立方(Face-Centered Cubic))結構之離子化合物。MgO之晶體結構內之點缺陷為蕭特基(Schottky)缺陷。當帶相反電荷之離子離開其等之晶格位置，產生空位時，則形成缺陷。就MgO而言，兼存在氧及鎂空位。然而，該燒結作用係藉氧空位之擴散而控制。添加摻質(例如NaF或LiF)至MgO可真正地調節該離子空位濃度，然而，例如Al2O3或SiO2可作為用於燒結作用之抑制劑。添加具有電荷低於+2之陽離子作為摻質(例如NaF或LiF)可增加燒結速率，然而添加具有電荷高於+2之陽離子(諸如氧化矽)會抑制燒結作用。MgO is an ionic compound having an FCC (Face-Centered Cubic) structure. The point defect in the crystal structure of MgO is a Schottky defect. Defects are formed when oppositely charged ions leave their lattice positions and create vacancies. In the case of MgO, both oxygen and magnesium vacancies are present. However, this sintering is controlled by the diffusion of oxygen vacancies. The addition of a dopant (e.g., NaF or LiF) to MgO can actually adjust the ion vacancy concentration, however, for example, Al 2 O 3 or SiO 2 can be used as an inhibitor for sintering. Adding a cation having a charge lower than +2 as a dopant (for example, NaF or LiF) increases the sintering rate, whereas addition of a cation having a charge higher than +2 (such as yttrium oxide) suppresses sintering.
如第1圖所示，添加少量膠態氧化矽至MgO，可在多次熱處置循環後改良該MgO之表面積安定性。有趣的是已添加矽酸鈉之試樣MGO-D並不會抑制這些特性，因為其含有Na+，Na+為具有電荷低於Na2+之陽離子，已預期於高溫下，Na+對表面積之維持具有不利影響。As shown in Figure 1, the addition of a small amount of colloidal cerium oxide to MgO improves the surface area stability of the MgO after multiple heat treatment cycles. Interestingly a sample of silicon was added sodium MGO-D does not inhibit these properties, because it contains Na +, Na + as a cationic charge of less than Na 2+, is expected to have a high temperature, Na + on the surface area The maintenance has an adverse effect.
業經發現添加呈化合物或其混合物形式之結構安定劑(諸如氧化矽、氧化鋁或氧化鋯)可以使該等MgO錠劑獲得熱安定性。根據文中揭示之實施例，結構安定劑可包括以下元素中之至少一種：Al、Si、Ti、Cr、Mn、Fe、Y、Zr、Mo及其等之組合。例如結構安定劑之使用量範圍可以是該催化劑重量之自約0.04至約40%(以該結構安定劑、催化金屬(群)、及載體材料(群)之總重計)。在某些實施例中，該結構安定劑係呈包括氧化矽、氧化鋁、及天然黏土(諸如高嶺石)中之至少一種的黏合劑形式。在其它實施例中，結構安定劑可包括MgAlO4及自Mg-Al水滑石之分解所形成的混合型金屬氧化物中之至少一種。It has been discovered that the addition of a structural stabilizer (such as cerium oxide, aluminum oxide or zirconia) in the form of a compound or a mixture thereof provides thermal stability to the MgO tablets. According to embodiments disclosed herein, the structural stabilizer may comprise at least one of the following elements: Al, Si, Ti, Cr, Mn, Fe, Y, Zr, Mo, and combinations thereof. For example, the amount of structural stabilizer may range from about 0.04 to about 40% by weight of the catalyst (based on the total weight of the structural stabilizer, catalytic metal (group), and support material (group)). In certain embodiments, the structural stabilizer is in the form of a binder comprising at least one of cerium oxide, aluminum oxide, and natural clay such as kaolinite. In other embodiments, the structural stabilizer may include at least one of MgAlO 4 and a mixed metal oxide formed from decomposition of Mg-Al hydrotalcite.
在試驗性測試時，具有5毫米或更大之有效直徑的氧化鎂雙鍵異構化反應催化劑顯示快速的去活化作用。活性之此種快速損失，不論是就新催化劑或再生催化劑而言，使該方法在經濟上的可行性變得很低且會抑制氧化鎂作為異構化反應催化劑的更廣泛用途。The magnesium oxide double bond isomerization catalyst having an effective diameter of 5 mm or more showed rapid deactivation upon experimental testing. Such rapid loss of activity, whether in terms of new or regenerated catalysts, makes the process economically less feasible and inhibits the wider use of magnesium oxide as a catalyst for isomerization.
已熟知較小催化劑直徑可改良特定催化劑之效能，其係藉減少該催化劑顆粒本身內之內部質量轉移抗性。較小直徑催化劑顆粒具有較短細孔，因此分子移動以抵達活性部位之距離較短。已知減少該顆粒有效直徑可改良一反應循環內該催化劑之總活性。It is well known that smaller catalyst diameters can improve the performance of a particular catalyst by reducing internal mass transfer resistance within the catalyst particles themselves. The smaller diameter catalyst particles have shorter pores so that the molecules move to a shorter distance to the active site. It is known that reducing the effective diameter of the particles improves the overall activity of the catalyst over a reaction cycle.
本申請案之發明者已非可預期地發現降低該等異構化反應催化劑之有效直徑事實上可減少隨時間所觀測之去活化作用。更特定地，本發明者已發現較小的有效直徑異構化反應催化劑可減少後續再生後之表面積的損失，因此可改良總效能。就併用異構化反應催化劑之複分解及僅異構化反應而言，的確如此。其優點包括較長的異構化反應催化劑循環時間、較高的總丁烯轉化率、及較高的產量，其包括當在乙烯存在下用於複分解反應器內可獲得較高丙烯產率。It has been unexpectedly discovered by the inventors of the present application that reducing the effective diameter of the isomerization catalysts can in fact reduce the deactivation observed over time. More specifically, the inventors have discovered that a smaller effective diameter isomerization catalyst can reduce the loss of surface area after subsequent regeneration, thereby improving overall efficiency. This is true in the case of the metathesis of the isomerization catalyst and the isomerization only reaction. Advantages include longer isomerization catalyst cycle times, higher total butene conversion, and higher yields, including higher propylene yields obtained in the metathesis reactor in the presence of ethylene.
該較小有效直徑之一預想不到的優點在甚至於未使用安定劑的情況下，仍可改良該MgO催化劑之安定性。第2A及2B圖表示在兩分別為5毫米及3毫米之不同粒度下，熱老化對該MgO催化劑之BET表面積的影響。於650℃下進行熱老化，費時24小時。就該MgO催化劑而言，於本650℃高溫下進行之熱老化被視為一項嚴厲的熱老化試驗。可清楚地瞭解於該3毫米之較小粒度下，在該嚴厲的熱老化後，該催化劑之BET表面積比該等5毫米顆粒之BET表面積高約55%(56米2/克對36米2/克)。An unexpected advantage of one of the smaller effective diameters is that the stability of the MgO catalyst can be improved even without the use of a stabilizer. Figures 2A and 2B show the effect of heat aging on the BET surface area of the MgO catalyst at two different particle sizes of 5 mm and 3 mm, respectively. Heat aging at 650 ° C took 24 hours. For the MgO catalyst, heat aging performed at a high temperature of 650 ° C is regarded as a severe heat aging test. It is clear that at this smaller particle size of 3 mm, after this severe heat aging, the BET surface area of the catalyst is about 55% higher than the BET surface area of the 5 mm particles (56 m 2 /g versus 36 m 2 ) /g).
該雙鍵異構化反應催化劑之較小有效直徑的影響為兩倍。首先，在丁烯之雙鍵異構化反應期間可發現已知更高的活性。然而，非可預期地，亦可改良該催化劑之安定性，其可得到較低的逐循環去活化作用。其可直接地解釋成經過多次循環仍可維持催化劑效能且因此可顯著增加該催化劑之壽命。The effect of the smaller effective diameter of the double bond isomerization catalyst is twice. First, a known higher activity can be found during the double bond isomerization reaction of butene. Unexpectedly, however, the stability of the catalyst can also be improved, which results in lower cycle-by-cycle deactivation. It can be directly explained that the catalyst performance can be maintained over multiple cycles and thus the life of the catalyst can be significantly increased.
根據文中揭示之實施例的異構化反應催化劑(諸如氧化鎂)可具有一小於5.0毫米之有效直徑；在其它實施例中，小於4.0毫米；在其它實施例中，小於3.2毫米；在其它實施例中，小於3.0毫米；在其它實施例中，小於2.8毫米；在其它實施例中，小於2.5毫米；在其它實施例中，小於2.0毫米；在其它實施例中，小於1.75毫米；在其它實施例中，小於1.5毫米；在其它實施例中，小於1.4毫米；在其它實施例中，小於1.0毫米；且在又其它實施例中小於0.7毫米。催化劑顆粒的有效直徑之定義為具有一類似的表面對體積比之等效球形物的直徑。The isomerization catalyst (such as magnesium oxide) according to embodiments disclosed herein may have an effective diameter of less than 5.0 mm; in other embodiments, less than 4.0 mm; in other embodiments, less than 3.2 mm; in other implementations In an embodiment, less than 3.0 mm; in other embodiments, less than 2.8 mm; in other embodiments, less than 2.5 mm; in other embodiments, less than 2.0 mm; in other embodiments, less than 1.75 mm; in other embodiments In the example, less than 1.5 mm; in other embodiments, less than 1.4 mm; in other embodiments, less than 1.0 mm; and in still other embodiments less than 0.7 mm. The effective diameter of the catalyst particles is defined as having a similar surface to volume ratio of the equivalent sphere diameter.
根據文中揭示之實施例的異構化反應催化劑可以呈小粒、擠出物等之形式。雖然在美國專利第6,875,901號中，粉末被認為是有用的催化劑形式，由於與在固定或填充床內使用粉末有關之高壓降，當異構化反應催化劑係與複分解催化劑摻合且在乙烯存在下用於商業固定床反應器或用於固定床異構化反應器時，在商業上並未使用粉末。因此，典型上不用於固定床反應器之粉末及更細緻材料明確地自根據文中揭示之實施例的催化劑排除。The isomerization catalyst according to the examples disclosed herein may be in the form of pellets, extrudates or the like. In U.S. Patent No. 6,875,901, the powder is considered to be a useful form of catalyst due to the high pressure drop associated with the use of powder in a fixed or packed bed, when the isomerization catalyst is blended with the metathesis catalyst and in the presence of ethylene. When used in commercial fixed bed reactors or in fixed bed isomerization reactors, no powder is commercially used. Thus, powders and finer materials that are typically not used in fixed bed reactors are expressly excluded from the catalysts according to the examples disclosed herein.
根據文中揭示之實施例的該等異構化反應催化劑為可用於固定床反應器或以催化劑蒸餾結構形成之催化劑，且因此在其它實施例中，呈小粒、球形物、擠出物等形式之異構化反應催化劑典型上可具有至少0.25毫米之有效直徑；在其它實施例中，至少0.3毫米；在其它實施例中，至少0.4毫米；且在又其它實施例中，至少0.5毫米，其中該等異構化反應催化劑可含有安定劑。The isomerization catalysts according to the embodiments disclosed herein are catalysts that can be used in fixed bed reactors or in catalyst distillation structures, and thus in other embodiments, in the form of pellets, spheres, extrudates, and the like. The isomerization catalyst can typically have an effective diameter of at least 0.25 mm; in other embodiments, at least 0.3 mm; in other embodiments, at least 0.4 mm; and in yet other embodiments, at least 0.5 mm, wherein The isomerization catalyst may contain a stabilizer.
此外，根據文中揭示之實施例的異構化反應催化劑為可用於固定床反應器或以催化蒸餾結構形式之催化劑，且因此呈小粒、球形物、擠出物等形式之異構化反應催化劑典型上可具有至少0.25毫米之有效直徑且當未使用安定劑時具有4.0毫米之最大有效直徑；在其它實施例中，至少0.5毫米且當未使用安定劑時，具有3.5毫米之最大有效直徑。可使用多種方法製備具有上述有效直徑之異構化反應催化劑。例如可製成具有一根據上述實施例之有效直徑的催化劑球形物。在其它實施例中，可以使較大直徑之催化劑獲得更高的表面對體積比。例如可製成空心圓柱體、三葉形顆粒、成形擠出物或具有較小直徑但較大長度之擠出物，例如可使用與美國專利第7,351,393號所揭示之擠出物類似的星形擠出物。與具同等有效直徑之球形物比較，這些成形催化劑之優點為可減少經由固定床所產生之壓降。在其它實施例中，該異構化反應催化劑可沈積在載體之表面上以形成“蛋殼(eggchell)”或在較大載體上形成活性成份之薄層(就蛋殼催化劑而言，可相對於僅經活性材料塗覆或浸漬之部份該催化劑而計算有效直徑)。可使用這些及其它技術以減少根據文中揭示之實施例之異構化反應催化劑的有效直徑。Furthermore, the isomerization catalyst according to the examples disclosed herein is a catalyst which can be used in a fixed bed reactor or in the form of a catalytic distillation structure, and thus is isomerized in the form of small particles, spheres, extrudates and the like. It may have an effective diameter of at least 0.25 mm and a maximum effective diameter of 4.0 mm when no stabilizer is used; in other embodiments, at least 0.5 mm and with a maximum effective diameter of 3.5 mm when no stabilizer is used. The isomerization catalyst having the above effective diameter can be prepared by various methods. For example, a catalyst sphere having an effective diameter according to the above embodiment can be produced. In other embodiments, larger diameter catalysts can be achieved with higher surface to volume ratios. For example, a hollow cylinder, a trilobal granule, a shaped extrudate or an extrudate having a smaller diameter but a larger length can be produced, for example, a star similar to the extrudate disclosed in U.S. Patent No. 7,351,393 can be used. Extrudate. These shaped catalysts have the advantage of reducing the pressure drop across the fixed bed compared to spheres of the same effective diameter. In other embodiments, the isomerization catalyst may be deposited on the surface of the support to form an "eggell" or a thin layer of active ingredient formed on a larger support (as opposed to eggshell catalysts, The effective diameter is calculated from the portion of the catalyst that is only coated or impregnated with the active material. These and other techniques can be used to reduce the effective diameter of the isomerization catalyst according to the examples disclosed herein.
文中揭示之雙鍵異構化反應催化劑可在固定床反應器、蒸餾柱反應器、及本項技藝中已知之其它反應器內用於使各種內烯烴(諸如2-丁烯)轉化成α-烯系化合物，諸如1-丁烯。雖然下文之描述係有關於丁烯，但是亦涵蓋2-戊烯轉化成1-戊烯、2-或3-己烯轉化成1-己烯、2-或3-庚烯轉化成1-庚烯等。更詳細地，根據文中揭示之實施例的催化劑可用於用以使2-丁烯轉化成1-丁烯之併發異構化反應、及可形成丙烯之2-丁烯與乙烯之複分解，其中該異構化反應可在乙烯存在下進行。The double bond isomerization catalysts disclosed herein can be used to convert various internal olefins, such as 2-butene, to a- in fixed bed reactors, distillation column reactors, and other reactors known in the art. An olefinic compound such as 1-butene. Although the following description relates to butene, it also covers the conversion of 2-pentene to 1-pentene, 2- or 3-hexene to 1-hexene, 2- or 3-heptene to 1-g. Alkene and the like. In more detail, the catalyst according to the examples disclosed herein can be used in the isomerization reaction for converting 2-butene to 1-butene, and the metathesis of 2-butene and ethylene which can form propylene, wherein The isomerization reaction can be carried out in the presence of ethylene.
文中揭示之饋至製程的混合型C4進料可包括C3至C6+烴，其包括，諸如得自蒸氣裂解器或流體催化裂解(FCC)單元之C4、C4至C5、及C4至C6裂解器流出物。亦可使用含C4烯烴之混合物的其它精煉烴物料流。當C3、C5及/或C6組份存在於該進料內時，該物料流可經預分餾以得到主要C4餾份、C4至C5餾份或C4至C6餾份。The mixed C 4 feed to the process disclosed herein may include C 3 to C 6+ hydrocarbons including, for example, C 4 , C 4 to C 5 from a vapor cracker or a fluid catalytic cracking (FCC) unit, And C 4 to C 6 cracker effluent. It may also be used other refinery hydrocarbon streams containing a mixture of C 4 olefins. When a C 3 , C 5 and/or C 6 component is present in the feed, the stream may be prefractionated to obtain a primary C 4 fraction, a C 4 to C 5 fraction or a C 4 to C 6 fraction. Share.
該進料物料流所含之C4組份可包括正-丁烷、異丁烷、異丁烯、1-丁烯、2-丁烯、及丁二烯。在某些實施例中，使該混合型C4進料經預處置以提供用於該複分解反應之富含正-丁烯進料。例如當丁二烯存在於該C4進料內時，可藉氫化反應或萃取而移除該丁二烯。在其它實施例中，在丁二烯氫化反應後或同時之該等混合型丁烯進料可接受氫異構化反應條件以將1-丁烯轉化成2-丁烯，且異丁烯係藉分餾而自2-丁烯物料流分離。The feed stream contained in the C 4 component may comprise n - butane, isobutane, isobutene, 1-butene, 2-butene, and butadiene. In certain embodiments, so that the mixed C 4 feed was pre-treated to provide for the metathesis reaction of enriched n - butene feed. For example, when butadiene is present in the C 4 feed, or may be extracted by the hydrogenation reaction of the butadiene is removed. In other embodiments, the mixed butene feed after or after the butadiene hydrogenation reaction may accept hydroisomerization conditions to convert 1-butene to 2-butene, and the isobutene is fractionated. And the separation from the 2-butene stream.
然後可將乙烯及正丁烯饋至含兼具複分解官能性及異構化反應官能性之催化劑的反應器內以將該1-丁烯之至少一部份轉化成2-丁烯，且使該2-丁烯與乙烯反應以形成可作為複分解產物之丙烯。可將該乙烯饋至反應器內，其饋入速率可以維持至少0.5之乙烯對正-丁烯的比率；在其它實施例中，該比率為至少1.0；在其它實施例中，該比率在自0.5至約2.5之範圍內；且在又其它實施例中，該比率為自約1.0或1.5至約2.0。該複分解反應器內所含之催化劑可以是任何已知複分解催化劑，其包括載體載第VIB族及第VIIB族金屬之氧化物。催化劑載體可具任何形狀且可包括氧化鋁、氧化矽、其等之混合物、氧化鋯、及沸石。除了該複分解催化劑外，該複分解反應器內所包含之催化劑包括具有如上述之有效直徑之雙鍵異構化反應催化劑，諸如氧化鎂或氧化鈣且此外，可或可不含有安定劑以在經過多次循環後可維持安定的雙鍵烯烴異構化反應活性。The ethylene and n-butene can then be fed to a reactor containing a catalyst having both metathesis functionality and isomerization functionality to convert at least a portion of the 1-butene to 2-butene and The 2-butene is reacted with ethylene to form propylene which is a metathesis product. The ethylene can be fed to the reactor at a feed rate that maintains a ratio of ethylene to n-butene of at least 0.5; in other embodiments, the ratio is at least 1.0; in other embodiments, the ratio is From 0.5 to about 2.5; and in still other embodiments, the ratio is from about 1.0 or 1.5 to about 2.0. The catalyst contained in the metathesis reactor may be any known metathesis catalyst comprising an oxide of a Group VIB and Group VIIB metal. The catalyst support can be of any shape and can include alumina, cerium oxide, mixtures thereof, zirconia, and zeolites. In addition to the metathesis catalyst, the catalyst contained in the metathesis reactor comprises a double bond isomerization catalyst having an effective diameter as described above, such as magnesium oxide or calcium oxide and, in addition, may or may not contain a stabilizer to pass through The stable double bond olefin isomerization activity can be maintained after the second cycle.
可使用根據文中揭示之實施例之催化劑的複分解方法之一實例闡明在第3圖中。可經由流動線路10將含正-丁烯、異丁烯、及烷烴之混合型C4物料流饋至分離器12，於其中該C4物料流可分離成至少兩餾份，其包括輕C4餾份(其包括異丁烯)、及重C4餾份(其包括正-丁烯)。該輕C4餾份係經由流動線路14而呈塔頂餾份形式自分離器12回收。An example of a metathesis process according to the catalysts of the examples disclosed herein can be illustrated in Figure 3. A mixed C 4 stream comprising n-butene, isobutylene, and an alkane may be fed to separator 12 via flow line 10, wherein the C 4 stream may be separated into at least two fractions including a light C 4 stream Parts (which include isobutylene), and heavy C 4 fractions (which include n-butene). The light fraction C 4 via line 14 and flow line as a form of overhead fraction recovered from the separator 12.
該重C4餾份可以呈塔底餾份形式經由流動線路16而回收並饋至複分解反應器18。乙烯可經由流動線路20及/或22共饋至反應器18內。複分解反應器18可含有一或多個具有根據文中揭示之習知複分解催化劑及異構化反應催化劑的床24。該複分解及異構化反應催化劑可在單一床內摻合或可放置在串連之反應器內，諸如藉連續將該等催化劑裝填在單一床內或將該等催化劑放置在反應器內之各床內。The weight C 4 fraction may be in the form of a bottoms fraction recovered via flow line 16 and fed to the metathesis reactor 18. Ethylene can be fed into the reactor 18 via flow lines 20 and/or 22. The metathesis reactor 18 can contain one or more beds 24 having conventional metathesis catalysts and isomerization catalysts as disclosed herein. The metathesis and isomerization catalysts may be blended in a single bed or may be placed in a series reactor, such as by continuously charging the catalysts in a single bed or placing the catalysts in the reactor. Inside the bed.
得自複分解反應器18之流出物可經由流動線路26饋至分離系統28，其可包括，例如用於將該流出物分離成碳數群組之蒸餾裝置。如所述，分離系統28可將該複分解產物分餾成至少4種餾份，其包括經由流動線路30而回收之含乙烯餾份、經由流動線路32而回收之含丙烯餾份、經由流動線路34而回收之C4餾份、及經由流動線路36而回收之C5+餾份。The effluent from the metathesis reactor 18 can be fed via a flow line 26 to a separation system 28, which can include, for example, a distillation unit for separating the effluent into a carbon number group. As described, the separation system 28 can fractionate the metathesis product into at least four fractions including a vinyl-containing fraction recovered via the flow line 30, a propylene-containing fraction recovered via the flow line 32, via the flow line 34. The recovered C 4 fraction and the C 5+ fraction recovered via the flow line 36.
可經由流動線路38而自該系統滌洗經由流動線路30而回收的部份該C2餾份。若必要，可以使經由流動線路30而回收之該乙烯的至少一部份呈乙烯進料形式經由流動線路22再循環至複分解反應器18。The system may be self-purging recovered via flow line 30 and part of the C 2 fraction via flow line 38. If necessary, at least a portion of the ethylene recovered via the flow line 30 can be recycled to the metathesis reactor 18 via the flow line 22 in the form of an ethylene feed.
可經由流動線路40而使經由流動34而回收之該C4餾份的至少一部份再循環至分離器12，且若必要可經由流動線路42而滌洗一部份。雖然未闡明，可另外使經由流動線路34而回收之該C4餾份再循環至複分解反應器18或至另外的下游加工單元。另外，當該烴物料流含有丁烯時，該方法可包括能在分離器12內分餾該烴進料前，氫化該等丁二烯之至少一部份的氫化階段。At least a portion of the flow via the line 40 and recovered via flow 34 of the C 4 fraction is recycled to the separator 12, and if necessary, may be part of a purging flow via a line 42. Although not illustrated, the C 4 fraction recovered via the flow line 34 may additionally be recycled to the metathesis reactor 18 or to another downstream processing unit. Additionally, when the hydrocarbon stream contains butene, the process can include hydrogenating a hydrogenation stage of at least a portion of the butadiene prior to fractionating the hydrocarbon feed in separator 12.
根據文中揭示之實施例的異構化反應催化劑亦可用於其中該異構化反應催化劑可暴露於乙烯之其它方法中，諸如除了別的以下，可揭示在美國專利第6,777,582號、第7,214,841號、及第7,223,895號之一或多者中的方法。The isomerization catalyst according to the examples disclosed herein can also be used in other processes in which the isomerization catalyst can be exposed to ethylene, such as, among others, U.S. Patent Nos. 6,777,582 and 7,214,841. And the method of one or more of No. 7,223,895.
添加氧化矽至5毫米市售MgO錠劑以作為結構安定劑。添加呈膠態氧化矽黏合劑形式或矽酸鈉形式之氧化矽至該等5毫米MgO錠劑。藉測量在多次熱循環後該等5毫米錠劑之BET表面積而測定該等錠劑之熱安定性。藉於550℃下在空氣中處理該等錠劑，費時12小時而進行各熱循環。Cerium oxide was added to a commercially available MgO tablet of 5 mm as a structural stabilizer. Cerium oxide in the form of a colloidal cerium oxide binder or sodium citrate is added to the 5 mm MgO tablets. The thermal stability of the tablets was determined by measuring the BET surface area of the 5 mm tablets after multiple thermal cycles. The heat treatment was carried out by treating the tablets in air at 550 ° C for 12 hours.
實例1Example 1
藉以含30重量%氧化矽(Ludox,AS-30,Aldrich chemicals)之膠態氧化矽溶液進行5毫米MgO錠劑(MGO)之濕浸漬而製成催化劑MGO-A。浸漬後，於120℃下乾燥該催化劑，費時24小時。藉XRF而測定之MGO-A的氧化矽含量為0.81重量%。於350℃下經標準BET除氣，費時16小時後，測定初BET表面積。於550℃下進行熱循環處理，費時12小時。經各熱處置後，在進行下一熱循環前，使該催化劑冷却至120℃，費時12小時。第1圖表示經該熱老化處理後，催化劑MGO-A之BET表面積降低。在第一次熱循環後發現BET表面積顯著減少。然而，經第二次熱循環後，MGO-A之BET表面積安定。相較下，在每一次循環(高至第4次熱循環)後，未經處置之5毫米MgO錠劑(MGO)仍持續損失BET表面積。The catalyst MGO-A was prepared by wet impregnation of a 5 mm MgO tablet (MGO) with a colloidal cerium oxide solution containing 30% by weight of cerium oxide (Ludox, AS-30, Aldrich chemicals). After impregnation, the catalyst was dried at 120 ° C for 24 hours. The cerium oxide content of MGO-A measured by XRF was 0.81% by weight. The initial BET surface area was measured after a standard BET degassing at 350 ° C for 16 hours. The thermal cycle treatment was carried out at 550 ° C and took 12 hours. After each heat treatment, the catalyst was cooled to 120 ° C for 12 hours before the next heat cycle. Figure 1 shows the reduction in the BET surface area of the catalyst MGO-A after the heat aging treatment. A significant reduction in BET surface area was found after the first thermal cycle. However, after the second thermal cycle, the BET surface area of MGO-A was stabilized. In contrast, the untreated 5 mm MgO tablet (MGO) continued to lose BET surface area after each cycle (up to the 4th thermal cycle).
實例2Example 2
以類似催化劑MGO-A之方法，藉以含30重量%氧化矽(Ludox,AS-30,Aldrich chemicals)之膠態氧化矽溶液進行5毫米MgO錠劑(MGO)之濕浸漬而製成催化劑MGO-B。浸漬後，於120℃下乾燥該催化劑，費時24小時。藉XRF而測定之MGO-B的氧化矽含量為0.81重量%。於350℃下進行標準BET除氣，費時16小時後，測定初BET表面積。於550℃下進行熱循環處理，費時12小時。經各熱處置後，在進行下一熱循環前，使該催化劑冷却至120℃，費時12小時。第1圖表示經熱老化處理後，催化劑X052-L2之BET表面積降低。在第一次熱循環後發現BET表面積顯著減少。然而，經第二次熱循環後，MGO-B之BET表面積安定。相較下，經每一次循環後，未經處置之5毫米MgO錠劑(MGO)仍持續損失BET表面積。The catalyst MGO- was prepared by wet impregnation of 5 mm MgO tablets (MGO) with a colloidal cerium oxide solution containing 30% by weight of cerium oxide (Ludox, AS-30, Aldrich chemicals) in a manner similar to the catalyst MGO-A. B. After impregnation, the catalyst was dried at 120 ° C for 24 hours. The cerium oxide content of MGO-B measured by XRF was 0.81% by weight. The standard BET degassing was carried out at 350 ° C and the initial BET surface area was measured after 16 hours. The thermal cycle treatment was carried out at 550 ° C and took 12 hours. After each heat treatment, the catalyst was cooled to 120 ° C for 12 hours before the next heat cycle. Figure 1 shows the reduction in the BET surface area of catalyst X052-L2 after heat aging treatment. A significant reduction in BET surface area was found after the first thermal cycle. However, after the second thermal cycle, the BET surface area of MGO-B is stable. In contrast, the untreated 5 mm MgO tablet (MGO) continued to lose the BET surface area after each cycle.
實例3Example 3
以類似實例1及2之方式藉以含30重量%氧化矽(Ludox,AS-30,Aldrich chemicals)之膠態氧化矽溶液進行5毫米MgO錠劑(MGO)之濕浸漬而製成催化劑MGO-C。浸漬後，於120℃下乾燥該催化劑，費時24小時。藉XRF而測定之MGO-C的氧化矽含量為1.14重量%。於350℃下進行標準BET除氣，費時16小時後，測定初BET表面積。於550℃下進行熱循環處理，費時12小時。經各熱處置後，在進行下一熱循環前使該催化劑冷却至120℃，費時12小時。第1圖表示經熱老化處理後，催化劑MGO-C之BET表面積降低。在第一次熱循環後發現BET表面積顯著減少。然而，在第二次熱循環後，MGO-C之BET表面積安定。相較下，經每一次循環後，未經處置的5毫米MgO錠劑(MGO)仍持續損失BET表面積。A catalyst MGO-C was prepared by wet impregnation of a 5 mm MgO tablet (MGO) with a colloidal cerium oxide solution containing 30% by weight of cerium oxide (Ludox, AS-30, Aldrich chemicals) in a manner similar to Examples 1 and 2. . After impregnation, the catalyst was dried at 120 ° C for 24 hours. The cerium oxide content of MGO-C measured by XRF was 1.14% by weight. The standard BET degassing was carried out at 350 ° C and the initial BET surface area was measured after 16 hours. The thermal cycle treatment was carried out at 550 ° C and took 12 hours. After each heat treatment, the catalyst was cooled to 120 ° C before the next heat cycle, which took 12 hours. Figure 1 shows the reduction in the BET surface area of the catalyst MGO-C after heat aging treatment. A significant reduction in BET surface area was found after the first thermal cycle. However, after the second thermal cycle, the BET surface area of MGO-C is stable. In contrast, the untreated 5 mm MgO tablets (MGO) continued to lose BET surface area after each cycle.
實例4Example 4
藉以矽酸鈉之溶液進行5毫米MgO錠劑(MGO)之濕浸漬而製成催化劑MGO-D。浸漬後，於120℃下乾燥該催化劑，費時24小時。藉XRF而測定之MGO-D的氧化矽含量為1.40重量%。於350℃下進行標準BET除氣，費時16小時後測定初BET表面積。於550℃下進行熱循環處理，費時12小時。經各熱處置後，在進行下一熱循環前，使該催化劑冷却至120℃，費時12小時。第1圖表示經熱老化處理後，催化劑MGO-D之BET表面積降低。經第一次熱循環後，發現BET表面積顯著減少。在每一次循環(至高第4次熱循環)時，MGO-D持續損失BET表面積。MGO-D含有Na+(其係為電荷低於Mg2+之陽離子)，已預期於高溫下，其對表面積之維持有不利影響。MGO-D與亦在每一次循環後會持續損失BET表面積的該5毫米MgO錠劑(MGO)類似。The catalyst MGO-D was prepared by wet impregnation of a 5 mm MgO tablet (MGO) with a solution of sodium citrate. After impregnation, the catalyst was dried at 120 ° C for 24 hours. The cerium oxide content of MGO-D measured by XRF was 1.40% by weight. Standard BET degassing was carried out at 350 ° C and the initial BET surface area was measured after 16 hours. The thermal cycle treatment was carried out at 550 ° C and took 12 hours. After each heat treatment, the catalyst was cooled to 120 ° C for 12 hours before the next heat cycle. Figure 1 shows the reduction in the BET surface area of the catalyst MGO-D after heat aging treatment. After the first thermal cycle, a significant reduction in BET surface area was found. At each cycle (up to the 4th thermal cycle), MGO-D continued to lose BET surface area. MGO-D contains Na + which is a cation having a lower charge than Mg 2+ and has been expected to have an adverse effect on the maintenance of surface area at elevated temperatures. MGO-D is similar to the 5 mm MgO tablet (MGO) which also continues to lose BET surface area after each cycle.
如上文實例所述，可藉添加結構安定劑而改善該MgO錠劑之結構安定性。As described in the examples above, the structural stability of the MgO tablet can be improved by the addition of a structural stabilizer.
亦業經發現使用較小有效直徑，甚至在未添加安定劑之情況下亦可改良該MgO催化劑的安定性。於650℃下進行熱老化處理，費時24小時，於650℃之本較高溫度下進行之熱老化處理被視為用於該MgO催化劑之嚴厲的熱老化試驗。It has also been found that the use of a smaller effective diameter improves the stability of the MgO catalyst even without the addition of a stabilizer. The heat aging treatment was carried out at 650 ° C for 24 hours, and the heat aging treatment at a relatively high temperature of 650 ° C was regarded as a severe heat aging test for the MgO catalyst.
實例5Example 5
藉於650℃下處理未使用安定劑所製成之5毫米MgO錠劑，費時24小時而進行嚴厲的熱老化處理。第2圖表示經嚴厲的熱老化處理後，該錠劑之孔隙體積以及BET表面積的變化。該5毫米MgO錠劑之初BET表面積為202米2/克且經熱老化處理後，其表面積減至36米2/克。而且，平均孔徑自3-10奈米之較廣範圍但較小直徑增至約28奈米。熱老化處理後，半最大全寬(FWHM)經測定為15.2奈米。A 5 mm MgO tablet made without using a stabilizer was treated at 650 ° C and subjected to severe heat aging treatment for 24 hours. Figure 2 shows the change in pore volume and BET surface area of the tablet after severe heat aging treatment. The 5 mm MgO tablet had an initial BET surface area of 202 m 2 /g and its surface area was reduced to 36 m 2 /g after heat aging treatment. Moreover, the average pore size increases from a wide range of 3-10 nm but a smaller diameter to about 28 nm. After heat aging treatment, the full width at half maximum (FWHM) was determined to be 15.2 nm.
實例6Example 6
使用相同MgO但未使用安定劑以製成3毫米MgO錠劑。藉於650℃下處理該錠劑，費時24小時而進行嚴厲的熱老化處理。第2圖表示經嚴厲的熱老化處理後，該錠劑之孔隙體積以及BET表面積的變化。該5毫米MgO之初BET表面積為183米2/克且經熱老化處理後，其表面積減至56米2/克。而且，平均孔徑自約8奈米之較小直徑增至約18奈米。經熱老化處理後，半最大全寬(FWHM)經測定為6.2奈米。比較實例5之該5毫米MgO錠劑及實例6之3毫米MgO錠劑，經嚴厲的熱老化處理後，較小有效直徑之錠劑可保有較高BET表面積。而且，與該5毫米錠劑比較，經熱老化處理後，該3毫米MgO錠劑之平均孔徑較低。如藉這兩種大小之半最大全寬(FWHM)的差異可知，與該5毫米MgO錠劑比較，經熱老化處理後，該3毫米MgO錠劑之細孔分佈亦較窄。與該5毫米錠劑之FWHM(15.2奈米)比較，該3毫米錠劑之FWHM為6.2奈米。The same MgO was used but no stabilizer was used to make a 3 mm MgO tablet. The tablet was treated at 650 ° C and subjected to severe heat aging treatment for 24 hours. Figure 2 shows the change in pore volume and BET surface area of the tablet after severe heat aging treatment. The 5 mm MgO had an initial BET surface area of 183 m 2 /g and its surface area was reduced to 56 m 2 /g after heat aging treatment. Moreover, the average pore size has increased from about 8 nanometers to about 18 nanometers. After heat aging treatment, the full width at half maximum (FWHM) was determined to be 6.2 nm. Comparing the 5 mm MgO tablet of Example 5 with the 3 mm MgO tablet of Example 6, after a severe heat aging treatment, the smaller effective diameter tablet retained a higher BET surface area. Moreover, the average pore size of the 3 mm MgO tablet was lower after heat aging treatment than the 5 mm tablet. By the difference in the half maximum width (FWHM) of the two sizes, the pore distribution of the 3 mm MgO tablet is also narrower after the heat aging treatment than the 5 mm MgO tablet. The FWHM of the 3 mm tablet was 6.2 nm compared to the FWHM (15.2 nm) of the 5 mm tablet.
如上文實例所述，藉使用具較低有效直徑之催化劑可改良MgO催化劑之安定性。As described in the examples above, the stability of the MgO catalyst can be improved by using a catalyst having a lower effective diameter.
在用於使1-丁烯轉化成2-丁烯之異構化反應的乙烯存在下且未使用複分解催化劑的情況下，比較根據文中揭示之實施例之氧化鎂催化劑的效能及習知氧化鎂催化劑之效能。除了進行催化劑之比較外，值得注意的是該異構化反應具平衡限制性；在平衡狀態下，當於600℉之溫度下操作時，純2-丁烯之C4進料的轉化率為約72至75%。其相當於在反應溫度下，約3.6之2-丁烯/1-丁烯平衡比。類似地，純1-丁烯之進料的轉化率為約22%才可達到該相同平衡比。Comparing the effectiveness of the magnesium oxide catalyst according to the examples disclosed herein with conventional magnesium oxide in the presence of ethylene for the isomerization of 1-butene to 2-butene without the use of metathesis catalysts The effectiveness of the catalyst. In addition to the comparison of the catalysts, it is worth noting that the isomerization reaction is equilibrium-limited; in equilibrium, when converted at a temperature of 600 °F, the conversion of the pure 2-butene C 4 feed is About 72 to 75%. It corresponds to a 2-butene/1-butene equilibrium ratio of about 3.6 at the reaction temperature. Similarly, the conversion of pure 1-butene is about 22% to achieve the same equilibrium ratio.
實例7Example 7
製成具有5.5之長度對直徑比之呈5毫米小粒的氧化鎂催化劑。將該催化劑裝填入異構化反應器內並於350℃下在無水惰性氣氛中加熱，費時60小時以移除實質上所有可影響活性之水及二氧化碳數量。A magnesium oxide catalyst having a length to diameter ratio of 5.5 to 5 mm pellets was prepared. The catalyst was loaded into an isomerization reactor and heated in an anhydrous inert atmosphere at 350 ° C for 60 hours to remove substantially all of the water and carbon dioxide that would affect the activity.
然後測試在乙烯存在下用於使1-丁烯轉化成2-丁烯之異構化反應之該催化劑的異構化活性。於400psig及600℉以及5.4之重量時空速度(WHSV)下進行該異構化反應。將乙烯及1-丁烯(其比率為1.8：1)饋至該反應器內。The isomerization activity of the catalyst for the isomerization of 1-butene to 2-butene in the presence of ethylene was then tested. The isomerization reaction was carried out at 400 psig and 600 °F and a weight hourly space velocity (WHSV) of 5.4. Ethylene and 1-butene (in a ratio of 1.8:1) were fed to the reactor.
實驗結果提供在第4圖內。先以如第4圖中所示之純1-丁烯(2-丁烯/1-丁烯比為零)開始，甚至於較低WHSV下，該催化劑昂初並不能達到平衡，其僅達到1.5之2-丁烯對1-丁烯之比率。該催化劑之活性隨著累積老化而快速降低。The experimental results are provided in Figure 4. Starting with pure 1-butene (2-butene/1-butene ratio of zero) as shown in Figure 4, even at lower WHSV, the catalyst does not reach equilibrium at first, it only reaches The ratio of 2-butene to 1-butene of 1.5. The activity of the catalyst decreases rapidly with cumulative aging.
實例8Example 8
製備具有2.9毫米有效直徑之氧化鎂催化劑(寬6長8之網狀結構)。將該催化劑裝填入異構化反應器內並於350℃下在無水惰性氣氛中加熱，費時60小時以移除實質上所有會影響活性之水及二氧化碳數量。A magnesium oxide catalyst having a effective diameter of 2.9 mm (a network structure having a width of 6 and a length of 8) was prepared. The catalyst was loaded into an isomerization reactor and heated in an anhydrous inert atmosphere at 350 ° C for 60 hours to remove substantially all of the water and carbon dioxide that would affect the activity.
然後在乙烯存在下，測試用於使1-丁烯轉化成2-丁烯之異構化反應之該催化劑的異構化活性。以和實例7相同的方式進行該實驗。The isomerization activity of the catalyst for the isomerization of 1-butene to 2-butene was then tested in the presence of ethylene. This experiment was carried out in the same manner as in Example 7.
實驗結果亦提供在第4圖內。在類似條件下，具有較小有效直徑(2.9毫米)之催化劑可首先達到平衡，但是活性隨時間而快速降低。The experimental results are also provided in Figure 4. Under similar conditions, a catalyst with a smaller effective diameter (2.9 mm) can first reach equilibrium, but the activity decreases rapidly over time.
實例9Example 9
製備具有1.35毫米之有效直徑的氧化鎂催化劑(寬12長18之網狀結構)。將該催化劑裝填入異構化反應器內並於350℃下在無水惰性氣氛中加熱，費時60小時以移除實質上所有會影響活性之水及二氧化碳數量。A magnesium oxide catalyst having a effective diameter of 1.35 mm (mesh structure of 12 lengths and 18 lengths) was prepared. The catalyst was loaded into an isomerization reactor and heated in an anhydrous inert atmosphere at 350 ° C for 60 hours to remove substantially all of the water and carbon dioxide that would affect the activity.
然後在乙烯存在下，測試用於使1-丁烯轉化成2-丁烯之異構化反應之該催化劑的異構化反應活性。於與實例7及8相同之條件下進行該異構化反應。The isomerization reactivity of the catalyst for the isomerization of 1-butene to 2-butene was then tested in the presence of ethylene. The isomerization reaction was carried out under the same conditions as in Examples 7 and 8.
該實驗之結果亦提供在第4圖內。如第4圖可知，具有1.35毫米之有效直徑的該等催化劑顆粒首先達到平衡，其產物之2-丁烯對1-丁烯的比率為約3.5。另外，該較小有效直徑之催化劑在經過一段長時間後仍可維持活性/效能，經約2400克正-丁烯進料/每克氧化鎂之累積老化後，其產物之2-丁烯對1-丁烯比率降至約3.3。The results of this experiment are also provided in Figure 4. As can be seen from Figure 4, the catalyst particles having an effective diameter of 1.35 mm were first equilibrated, and the ratio of 2-butene to 1-butene of the product was about 3.5. In addition, the smaller effective diameter catalyst maintains activity/efficiency after a prolonged period of time, after the cumulative aging of about 2400 grams of n-butene feed per gram of magnesium oxide, the 2-butene pair of the product The 1-butene ratio fell to about 3.3.
實例10Example 10
製備具有0.64毫米之有效直徑的氧化鎂催化劑(寬20長10網狀結構)。將該催化劑裝填入異構化反應器內並於350℃下在無水惰性氣氛中加熱，費時60小時以移除實質上所有會影響活性之水及二氧化碳數量。A magnesium oxide catalyst (width 20 long 10 mesh structure) having an effective diameter of 0.64 mm was prepared. The catalyst was loaded into an isomerization reactor and heated in an anhydrous inert atmosphere at 350 ° C for 60 hours to remove substantially all of the water and carbon dioxide that would affect the activity.
然後在乙烯存在下測試用於使1-丁烯轉化成2-丁烯之異構化反應之該催化劑的異構化反應活性。於與實例7-9相同的條件下進行該異構化反應。The isomerization reactivity of the catalyst for the isomerization reaction of 1-butene to 2-butene was then tested in the presence of ethylene. The isomerization reaction was carried out under the same conditions as in Examples 7-9.
實驗結果亦提供在第4圖內。如第4圖可知，該等具有0.64毫米之有效直徑的催化劑顆粒可首先達到平衡，其產物之2-丁烯對1-丁烯比為約3.5。另外，經過一段長時間後，該較少有效直徑的催化劑仍可維持活性/效能，經過約4000克正-丁烯進料/每克氧化鎂之累積老化後，其產物之2-丁烯對1-丁烯比減至約3.2。The experimental results are also provided in Figure 4. As can be seen from Fig. 4, the catalyst particles having an effective diameter of 0.64 mm can be first balanced, and the product has a 2-butene to 1-butene ratio of about 3.5. In addition, after a long period of time, the less effective diameter of the catalyst maintains activity/efficiency, after a cumulative aging of about 4000 grams of n-butene feed per gram of magnesium oxide, the 2-butene pair of the product The 1-butene ratio was reduced to about 3.2.
熟悉本項技藝者可預期如根據減少的質量轉移極限，具有較小有效直徑之催化劑能改善用於使1-丁烯轉化成2-丁烯之異構化反應的動力學。該減少的質量轉移抗性會導致如上文觀測到之作用，亦即使達到平衡之異構化反應的活性更長時間地增加。Those skilled in the art will appreciate that a catalyst having a smaller effective diameter can improve the kinetics of the isomerization reaction for the conversion of 1-butene to 2-butene, as per the reduced mass transfer limit. This reduced mass transfer resistance results in an effect as observed above, and even if the activity of the equilibrium isomerization reaction is increased for a longer period of time.
然而，如上述，除了在一次循環內之活性外，使用具較小有效直徑之MgO催化劑非可預期地發現經過多次循環後，催化劑活性可改良。However, as described above, in addition to the activity in one cycle, the use of a MgO catalyst having a smaller effective diameter is unpredictably found to improve the catalyst activity after repeated cycles.
業經發現經由使用較小的有效直徑，可改良該MgO催化劑之安定性。亦業經發現經由使用較小的有效直徑，可改良該MgO催化劑耐逐循環再生之安定性。在可製備丙烯之複分解條件下兼測試未添加安定劑之5毫米MgO錠劑及3毫米MgO錠劑，其兼包括使1-丁烯轉化成2-丁烯之異構化反應、及可形成丙烯之乙烯與2-丁烯所進行的複分解。It has been found that the stability of the MgO catalyst can be improved by using a smaller effective diameter. It has also been found that by using a smaller effective diameter, the stability of the MgO catalyst against cycle regeneration can be improved. The 5 mm MgO tablet and the 3 mm MgO tablet without the stabilizer added are tested under the metathesis conditions for preparing propylene, which also includes the isomerization reaction for converting 1-butene to 2-butene, and can be formed. The metathesis of ethylene and 2-butene by propylene.
由於該複分解反應僅發生在2-丁烯與乙烯(1-丁烯及乙烯為非生產性反應)之間，所以一僅由乙烯及1-丁烯所組成之進料可提供達到特定複分解轉化所需之最高異構化反應效率。此外，根據該進料純度，在1-丁烯與2-丁烯之間有額外的相互轉換作用，若達到平衡，則在該排出物內可得到約3.6之2-丁烯對1-丁烯比。若於反應溫度下，該進料之1-丁烯含量比率高於平衡比，則在一次循環內及經過多次循環後本比率會隨該異構化反應催化劑老化而降低。Since the metathesis reaction only occurs between 2-butene and ethylene (1-butene and ethylene are unproductive), a feed consisting solely of ethylene and 1-butene provides specific metathesis conversion. The highest isomerization reaction efficiency required. In addition, depending on the feed purity, there is an additional interconversion between 1-butene and 2-butene. If equilibrium is reached, about 3.6 2-butene to 1-but can be obtained in the effluent. Obi ratio. If the 1-butene content ratio of the feed is higher than the equilibrium ratio at the reaction temperature, the ratio will decrease as the isomerization catalyst ages in one cycle and after multiple cycles.
實例11Example 11
在含該等用於異構化反應之MgO錠劑、及用於複分解之WO3/SiO2催化劑的混合床內進行試驗。該試驗係於315℃之溫度、12之WHSV、及400psig之壓力下進行。該進料係由純1-丁烯及乙烯(乙烯/1-丁烯之莫耳比為1.8)所組成。以相同方式製成兩種催化劑，但其例外為其中之一者經壓製成具有3毫米有效直徑之錠劑，而另一者經壓製成具有5毫米有效直徑之錠劑。然後使其等各進行相同的測試方案。該測試方案係由以下順序所組成：The test was carried out in a mixed bed containing the MgO tablets for isomerization and the WO 3 /SiO 2 catalyst for metathesis. The test was carried out at a temperature of 315 ° C, a WHSV of 12, and a pressure of 400 psig. The feed consisted of pure 1-butene and ethylene (ethylene/1-butene molar ratio of 1.8). Two catalysts were prepared in the same manner except that one of them was pressed into a tablet having an effective diameter of 3 mm, and the other was pressed into a tablet having an effective diameter of 5 mm. Then let them wait for the same test protocol. The test plan consists of the following sequence:
1. 如上述，活化該催化劑並於315℃下接受反應循環。使該反應進行直到如藉1-丁烯轉化率之損失所顯示而注意到去活化反應為止。1. Activate the catalyst as described above and accept the reaction cycle at 315 °C. The reaction is allowed to proceed until the deactivation reaction is noted as indicated by the loss of 1-butene conversion.
2. 藉燃燒於500℃下所沈積之焦碳，繼而於550℃下進行N2滌洗而再生該催化劑。然後冷却該催化劑並活化以便用於下一反應循環。2. The catalyst was regenerated by burning coke deposited at 500 ° C followed by N 2 scrubbing at 550 °C. The catalyst is then cooled and activated for use in the next reaction cycle.
3. 完成24小時之第二反應循環以將部份焦碳沈積在該催化劑上。經24小時後，如步驟2所述，再生本催化劑。3. Complete a 24 hour second reaction cycle to deposit a portion of the coke on the catalyst. After 24 hours, the catalyst was regenerated as described in step 2.
4. 再重複步驟3兩次以因此形成已經歷總共4次循環之催化劑混合物。4. Repeat step 3 twice more to form a catalyst mixture that has been subjected to a total of 4 cycles.
5. 然後完成第5次反應循環，使該反應進行，直到如藉1-丁烯轉化率之損失所顯示而注意到去活化作用為止。5. The 5th reaction cycle is then completed and the reaction is allowed to proceed until deactivation is noted as indicated by the loss of 1-butene conversion.
第5圖中顯示該3毫米MgO錠劑及5毫米錠劑之循環1-與循環5間的1-丁烯轉化率。轉化率係以相對的1-丁烯轉化率計表示。例如該平衡1-丁烯轉化率係以1.0之相對轉化率表示。Figure 5 shows the 1-butene conversion between Cycle 1 and Cycle 5 for the 3 mm MgO tablet and 5 mm tablet. Conversion is expressed as relative 1-butene conversion. For example, the equilibrium 1-butene conversion is expressed as a relative conversion of 1.0.
可知該3毫米MgO錠劑之循環1效能接***衡且安定性高達已饋入1200千克正-丁烯/每千克催化劑之累積老化。在累積老化之進一步增加的情況下，發現催化劑去活化作用且於已饋入2600千克正-丁烯/每千克催化劑之累積老化下，發現0.66相對1-丁烯轉化率。進一步可知該3毫米MgO錠劑之循環5效能稍低於平衡且很類似該循環1轉化率。而且，循環5之1-丁烯轉化率的安定性高達已饋入1100千克正-丁烯/每千克催化劑之累積老化。在累積老化之進一步增加下，發現催化劑去活化作用且於已饋入1800千克正-丁烯/每千克催化劑之累積老化下，發現0.81相對1-丁烯轉化率。It can be seen that the cycle 1 performance of the 3 mm MgO tablet is close to equilibrium and the stability is as high as the cumulative aging of 1200 kg of n-butene per kg of catalyst. In the case of a further increase in cumulative aging, catalyst deactivation was found and 0.66 relative 1-butene conversion was found under the cumulative aging that had been fed 2600 kg n-butene per kg catalyst. It is further known that the cycle 5 performance of the 3 mm MgO tablet is slightly lower than equilibrium and very similar to the cycle 1 conversion. Moreover, the stability of the 1-butene conversion of Cycle 5 is as high as the cumulative aging of 1100 kg of n-butene per kg of catalyst fed. Under a further increase in cumulative aging, catalyst deactivation was found and 0.81 relative 1-butene conversion was found under cumulative aging that had been fed 1800 kg n-butene per kg catalyst.
就該5毫米錠劑而言，可知該5毫米MgO錠劑之循環1效能遠低於平衡(0.91之相對1-丁烯轉化率)。而且，該試驗從頭至尾，在該5毫米MgO錠劑上進行之循環1的1-丁烯轉化率顯著低於在該3毫米MgO錠劑上進行之循環1的1-丁烯轉化率。循環1中之該5毫米MgO的1-丁烯轉化率從未具安定性且自操作開始，持續地發生去活化作用。於已饋入1975千克正-丁烯/每千克催化劑之累積老化下，發現僅0.46相對1-丁烯轉化率。For the 5 mm tablet, it is known that the cycle 1 performance of the 5 mm MgO tablet is much lower than the equilibrium (0.91 relative 1-butene conversion). Moreover, from the beginning to the end of the test, the 1-butene conversion of the cycle 1 carried out on the 5 mm MgO tablet was significantly lower than the 1-butene conversion of the cycle 1 performed on the 3 mm MgO tablet. The 1-butene conversion of the 5 mm MgO in Cycle 1 has never been stable and has been deactivated continuously since the start of operation. At a cumulative age of 1975 kg of n-butene per kg of catalyst fed, a conversion of only 0.46 relative to 1-butene was found.
可知該5毫米MgO錠劑之循環5效能亦遠低於平衡(0.90之相對1-丁烯轉化率)。就各別之第5次循環而言，該5毫米MgO錠劑之去活化速率亦遠高於該3毫米MgO錠劑。循環5中之該5毫米MgO錠劑的去活化速率亦顯著高於其在第一循環內之去活化速率。其與該3毫米MgO錠劑之循環5結果顯然有大不同。與該3毫米MgO錠劑比較，就該5毫米MgO錠劑而言，自循環1至循環5之催化劑效能的變質非常嚴重。於已饋入1044千克正-丁烯/每公斤催化劑之累積老化下，發現僅0.44相對1-丁烯轉化率。It can be seen that the cycle 5 performance of the 5 mm MgO tablet is also much lower than the equilibrium (0.90 relative 1-butene conversion). For each of the 5th cycles, the deactivation rate of the 5 mm MgO tablet was also much higher than the 3 mm MgO tablet. The deactivation rate of the 5 mm MgO tablet in Cycle 5 was also significantly higher than its deactivation rate in the first cycle. It is clearly quite different from the cycle 5 result of the 3 mm MgO tablet. Compared to the 3 mm MgO tablet, the deterioration of the catalyst performance from cycle 1 to cycle 5 was very severe with respect to the 5 mm MgO tablet. At a cumulative age of 1044 kg n-butene per kg catalyst, only 0.44 relative 1-butene conversion was found.
熟悉本項技藝者可預期如基於減少的質量轉移局限，該等具有較小有效直徑之催化劑可改良使1-丁烯轉化成2-丁烯之異構化反應的動力學。其可解釋循環1之該3毫米與5毫米有效直徑間的效能差異。然而，使用具有較小有效直徑之MgO催化劑非可預期地發現在一循環其間該等去活化速率亦顯著地降低。亦發現藉使用具較小有效直徑之催化劑可減少逐循環效能變質。其並不能由較低有效直徑之質量轉移抗性的單純減少來加以解釋。Those skilled in the art will appreciate that such catalysts having smaller effective diameters may improve the kinetics of the isomerization of 1-butene to 2-butene, as based on reduced mass transfer limitations. It explains the difference in potency between the 3 mm and 5 mm effective diameters of Cycle 1. However, the use of MgO catalysts having smaller effective diameters was unpredictably found to also be significantly reduced during a cycle. It has also been found that by using a catalyst having a smaller effective diameter, cycle-by-cycle performance deterioration can be reduced. It cannot be explained by a simple reduction in the mass transfer resistance of the lower effective diameter.
如上述，文中揭示之實施例提供用於使1-丁烯轉化成2-丁烯之該異構化反應、及可形成丙烯之2-丁烯與乙烯所進行之複分解的催化劑。具有小於約3.2毫米之有效直徑的文中所揭示之異構化反應催化劑甚至在乙烯存在下可顯示用於使1-丁烯轉化成2-丁烯之該異構化反應的優異活性。另外，此等催化劑在乙烯存在下經過一段時間後仍顯示減少的去活化速率、及較長的催化劑壽命。有利的是，根據文中揭示之實施例的催化劑可改良該合併異構化反應/複分解反應器之總效能，其包括較長的異構化反應催化劑循環時間、較高的總丁烯轉化率、及較高的製造量，其包括當在乙烯存在下用於複分解反應器內可獲得之更高丙烯產率。As described above, the examples disclosed herein provide a catalyst for the isomerization reaction for converting 1-butene to 2-butene, and metathesis of 2-butene and ethylene which can form propylene. The isomerization catalyst disclosed herein having an effective diameter of less than about 3.2 mm exhibits excellent activity for the isomerization reaction for converting 1-butene to 2-butene even in the presence of ethylene. Additionally, such catalysts exhibit reduced deactivation rates and longer catalyst life over a period of time in the presence of ethylene. Advantageously, the catalyst according to the examples disclosed herein can improve the overall efficiency of the combined isomerization/metathesis reactor, including longer isomerization catalyst cycle times, higher total butene conversion, And higher manufacturing levels, including higher propylene yields available in the metathesis reactor in the presence of ethylene.
雖然該揭示文包括有限的實施例數，但是熟悉本項技藝者根據本揭示文之優點，可瞭解只要不違背本揭示文之範圍可想出其它實施例。因此，該範圍應僅受限於附加申請專利範圍。While the disclosure includes a limited number of embodiments, it will be appreciated by those skilled in the art that the present invention can be devised without departing from the scope of the disclosure. Therefore, the scope should be limited only by the scope of the additional patent application.
10、14、16、20、22、26、30、32、34、36、38、40、42．．．流動線路10, 14, 16, 20, 22, 26, 30, 32, 34, 36, 38, 40, 42. . . Mobile line
12．．．分離器12. . . Splitter
18．．．複分解反應器18. . . Metathesis reactor
24．．．複分解催化劑及異構化反應催化劑床twenty four. . . Metathesis catalyst and isomerization catalyst bed
28．．．分離系統28. . . Separation system
第1圖為以熱老化為變數，含結構安定劑之MgO錠劑之BET表面積之變化的圖示。Figure 1 is a graphical representation of the change in BET surface area of a MgO tablet containing a structural stabilizer as a function of heat aging.
第2A及2B圖為於650℃下經激烈的熱老化後，具不同尺寸之MgO錠劑之BET表面積及細孔結構的變化之圖示(2A=5毫米，2B=3毫米催化劑有效直徑)。Figures 2A and 2B are graphical representations of changes in BET surface area and pore structure of MgO tablets of different sizes after intense heat aging at 650 °C (2A = 5 mm, 2B = 3 mm effective diameter of catalyst) .
第3圖為根據文中揭示之實施例，使用催化劑進行異構化反應及複分解之方法的簡化製程流程圖。Figure 3 is a simplified process flow diagram of a method for isomerization and metathesis using a catalyst in accordance with an embodiment disclosed herein.
第4圖為與當在乙烯存在下使用典型氧化鎂催化劑比較，根據文中揭示之實施例，經過一段時間後，催化劑之催化劑活性的圖示。Figure 4 is a graphical representation of the catalyst activity of the catalyst over a period of time in accordance with the examples disclosed herein when compared to the use of a typical magnesium oxide catalyst in the presence of ethylene.
第5圖為在用於丙烯之複分解的最初及第5次循環中，不同程度之MgO顆粒之1-丁烯轉化率對累積老化的比較之圖示。Figure 5 is a graphical representation of the comparison of 1-butene conversion versus cumulative aging for varying degrees of MgO particles in the first and fifth cycles of metathesis of propylene.
10、14、16、20、22、26、30、32、34、36、38、40、42．．．流動線路10, 14, 16, 20, 22, 26, 30, 32, 34, 36, 38, 40, 42. . . Mobile line
12．．．分離器12. . . Splitter
18．．．複分解反應器18. . . Metathesis reactor
24．．．複分解催化劑及異構化反應催化劑床twenty four. . . Metathesis catalyst and isomerization catalyst bed
28．．．分離系統28. . . Separation system
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Families Citing this family (57)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102361840A (en) * | 2009-04-01 | 2012-02-22 | 三井化学株式会社 | Method for manufacturing olefin |
| US8343885B2 (en) * | 2010-12-21 | 2013-01-01 | Basf Corporation | Isomerization catalysts |
| US9120736B2 (en) * | 2011-04-20 | 2015-09-01 | Cognis Ip Management Gmbh | Method for producing unsaturated compounds |
| US20130340327A1 (en) * | 2012-06-26 | 2013-12-26 | Basf Se | Process For Preparing Unsaturated Compounds |
| US9695096B2 (en) | 2012-07-12 | 2017-07-04 | Lummus Technology Inc. | More energy efficient C5 hydrogenation process |
| CN103539618B (en) * | 2012-07-12 | 2015-07-08 | 中国石油化工股份有限公司 | Hexene double-bond isomerization method |
| MX360442B (en) * | 2012-09-14 | 2018-10-31 | Lummus Technology Inc | Propylene via metathesis with low or no ethylene. |
| KR101971261B1 (en) * | 2012-10-06 | 2019-04-22 | 쿠라리안토 쇼쿠바이 가부시키가이샤 | Catalyst mixture for olefin metathesis reactions, method for producing same, and method for producing propylene using same |
| CN103772115B (en) * | 2012-10-25 | 2015-08-12 | 中国石油化工股份有限公司 | Iso-butylene produces the method for tetramethyl-ethylene |
| US20140121429A1 (en) * | 2012-10-30 | 2014-05-01 | Lyondell Chemical Technology, L.P. | Propylene production process with heavies recycle |
| WO2014077997A1 (en) | 2012-11-19 | 2014-05-22 | Lummus Technology Inc. | Process to produce linear pentenes and metathesis thereof |
| US9688591B2 (en) * | 2013-01-10 | 2017-06-27 | Equistar Chemicals, Lp | Ethylene separation process |
| US20140235914A1 (en) * | 2013-02-19 | 2014-08-21 | Basf Corporation | Eggshell Catalyst Composites Containing Tungsten Oxide or Tungsten Oxide Hydrate |
| CN104107688B (en) * | 2013-04-16 | 2016-12-28 | 中国石油化工股份有限公司 | Sheet metal oxide catalyst and preparation method thereof |
| EP2829317A1 (en) * | 2013-07-23 | 2015-01-28 | Borealis AG | Improved catalyst bed configuration for olefin production |
| AU2014317053B2 (en) * | 2013-09-05 | 2018-04-19 | Linde Aktiengesellschaft | Method for producing hydrocarbon products |
| EP2862629A1 (en) | 2013-10-15 | 2015-04-22 | Borealis AG | Catalyst and process for olefin metathesis reaction |
| CN104549351B (en) * | 2013-10-28 | 2017-10-27 | 中国石油化工股份有限公司 | Isomerization catalyst |
| CN104549212B (en) * | 2013-10-28 | 2017-03-15 | 中国石油化工股份有限公司 | Double bond isomerizing catalyst |
| CN104549295B (en) * | 2013-10-28 | 2017-09-15 | 中国石油化工股份有限公司 | Olefin isomerization catalyst |
| EP2873459A1 (en) | 2013-11-14 | 2015-05-20 | Borealis AG | Catalyst bed configuration for olefin conversion and process for obtaining olefins |
| CN111362771A (en) * | 2013-11-20 | 2020-07-03 | 鲁姆斯科技公司 | Olefin double bond isomerization catalyst with high toxicity resistance |
| EP2886189A1 (en) | 2013-12-20 | 2015-06-24 | Borealis AG | Process for olefin production by metathesis and reactor system therefor |
| CN103804227B (en) * | 2014-02-17 | 2016-02-10 | 重庆中平紫光科技发展有限公司 | A kind of method of alkene nitrile mixed solution By Direct Isomerization synthesis 2-methyl-2-butene nitrile |
| TWI628273B (en) | 2015-01-29 | 2018-07-01 | 魯瑪斯科技股份有限公司 | Producing c5 olefins from steam cracker c5 feeds |
| WO2016149507A1 (en) * | 2015-03-17 | 2016-09-22 | Siluria Technologies, Inc. | Oxidative coupling of methane methods and systems |
| WO2017003812A1 (en) | 2015-07-02 | 2017-01-05 | Saudi Arabian Oil Company | Dual catalyst system for propylene production |
| KR102592369B1 (en) | 2015-07-02 | 2023-10-25 | 사우디 아라비안 오일 컴퍼니 | Preparation of propylene using mesoporous silica foam metathesis catalyst |
| JP6803861B2 (en) | 2015-07-02 | 2020-12-23 | サウジ アラビアン オイル カンパニーＳａｕｄｉ Ａｒａｂｉａｎ Ｏｉｌ Ｃｏｍｐａｎｙ | Systems and methods for producing propylene |
| CN107709276B (en) | 2015-07-02 | 2020-10-13 | 沙特***石油公司 | System and process for producing propylene |
| US10125062B2 (en) | 2015-11-06 | 2018-11-13 | Lyondell Chemical Technology, L.P. | Propylene production processes and catalyst systems for use therein |
| US10010870B2 (en) * | 2015-11-12 | 2018-07-03 | Saudi Arabian Oil Company | Synthesis of catalytic materials for metathesis and isomerization reactions and other catalytic applications via well controlled aerosol processing |
| CN114539016A (en) | 2016-01-29 | 2022-05-27 | 利安德化学技术有限公司 | Catalyst and process for producing propylene from ethylene and butene |
| US10329225B2 (en) | 2017-01-20 | 2019-06-25 | Saudi Arabian Oil Company | Dual catalyst processes and systems for propylene production |
| US10550048B2 (en) | 2017-01-20 | 2020-02-04 | Saudi Arabian Oil Company | Multiple-stage catalyst system for self-metathesis with controlled isomerization and cracking |
| US10934231B2 (en) | 2017-01-20 | 2021-03-02 | Saudi Arabian Oil Company | Multiple-stage catalyst systems and processes for propene production |
| US10407363B2 (en) | 2017-08-16 | 2019-09-10 | Saudi Arabian Oil Company | Steam-less process for converting butenes to 1,3-butadiene |
| FR3084361A1 (en) | 2018-07-25 | 2020-01-31 | IFP Energies Nouvelles | PROCESS FOR THE METATHESIS OF OLEFINS USING A CATALYST CONTAINING SILICON, MOLYBDENE AND SULFUR |
| FR3084362A1 (en) | 2018-07-25 | 2020-01-31 | IFP Energies Nouvelles | PROCESS FOR THE METATHESIS OF OLEFINS USING A CATALYST CONTAINING SILICON, MOLYBDENE AND AN ALKALINE ELEMENT |
| FR3084363B1 (en) | 2018-07-25 | 2020-08-07 | Ifp Energies Now | OLEFINS METATHESIS PROCESS USING A CATALYST CONTAINING SILICON, MOLYBDENE AND AN ALKALINE ELEMENT |
| US10961171B2 (en) | 2018-10-10 | 2021-03-30 | Saudi Arabian Oil Company | Catalysts systems that include metal co-catalysts for the production of propylene |
| US11242299B2 (en) | 2018-10-10 | 2022-02-08 | Saudi Arabian Oil Company | Catalyst systems that include metal oxide co-catalysts for the production of propylene |
| JP2020089866A (en) * | 2018-12-07 | 2020-06-11 | クラリアント触媒株式会社 | Olefin isomerization catalyst and method for producing the same, method for producing 2-butene and propylene production method using the same |
| CN110201713B (en) * | 2019-06-17 | 2022-03-11 | 万华化学集团股份有限公司 | Catalyst, preparation method thereof and application thereof in olefin isomerization reaction |
| FR3103192A1 (en) | 2019-11-15 | 2021-05-21 | IFP Energies Nouvelles | OLEFINS METATHESIS PROCESS USING A HIGH ALKALINE CATALYST CONTAINING SILICON, MOLYBDENE |
| CN110922291B (en) * | 2019-11-22 | 2021-09-21 | 中国石油大学(北京) | Method for producing propylene by using bio-based ethanol and butanol mixed solution |
| US11517892B2 (en) * | 2019-12-03 | 2022-12-06 | Saudi Arabian Oil Company | Methods of producing isomerization catalysts |
| US11311869B2 (en) | 2019-12-03 | 2022-04-26 | Saudi Arabian Oil Company | Methods of producing isomerization catalysts |
| US11339332B2 (en) | 2020-01-29 | 2022-05-24 | Saudi Arabian Oil Company | Systems and processes integrating fluidized catalytic cracking with metathesis for producing olefins |
| US11572516B2 (en) | 2020-03-26 | 2023-02-07 | Saudi Arabian Oil Company | Systems and processes integrating steam cracking with dual catalyst metathesis for producing olefins |
| US11420915B2 (en) * | 2020-06-11 | 2022-08-23 | Saudi Arabian Oil Company | Red mud as a catalyst for the isomerization of olefins |
| US11427519B2 (en) | 2021-01-04 | 2022-08-30 | Saudi Arabian Oil Company | Acid modified red mud as a catalyst for olefin isomerization |
| US11679378B2 (en) | 2021-02-25 | 2023-06-20 | Saudi Arabian Oil Company | Methods of producing isomerization catalysts |
| US11319263B1 (en) | 2021-03-03 | 2022-05-03 | Saudi Arabian Oil Company | Methods for low temperature production of 1-butene |
| US11845705B2 (en) | 2021-08-17 | 2023-12-19 | Saudi Arabian Oil Company | Processes integrating hydrocarbon cracking with metathesis for producing propene |
| WO2023245045A1 (en) * | 2022-06-17 | 2023-12-21 | Dow Global Technologies Llc | Processes for converting unsaturated polyethylene to alkene products |
| WO2023245043A1 (en) * | 2022-06-17 | 2023-12-21 | Dow Global Technologies Llc | Processes for converting saturated polyethylene to alkene products |
Family Cites Families (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2947708A (en) * | 1957-04-08 | 1960-08-02 | Socony Mobil Oil Co Inc | Method for manufacturing a catalyst comprising a cogelled composite of silica and magnesia |
| US3915897A (en) * | 1971-08-30 | 1975-10-28 | Phillips Petroleum Co | Olefin disproportionation catalyst |
| IT1190839B (en) * | 1982-05-27 | 1988-02-24 | Anic Spa | PROCEDURE FOR THE ISOMERIZATION OF BOND OF THE OLEFINS |
| US4684760A (en) * | 1986-02-24 | 1987-08-04 | Phillips Petroleum Company | Catalyst compositions useful for olefin isomerization and disproportionation |
| GB8612687D0 (en) * | 1986-05-23 | 1986-07-02 | Shell Int Research | Stabilized magnesia |
| CA1329464C (en) * | 1988-08-12 | 1994-05-17 | Gohfu Suzukamo | Solid base, process for producing the same and process of preparing internal olefins |
| JPH0686395B2 (en) * | 1988-08-12 | 1994-11-02 | 住友化学工業株式会社 | Internal olefin production method |
| US5120894A (en) * | 1988-09-19 | 1992-06-09 | Lyondell Petrochemical Company | Olefin conversion process |
| US5300718A (en) * | 1988-09-19 | 1994-04-05 | Lyondell Petrochemical Company | Olefin conversion process |
| US5087780A (en) * | 1988-10-31 | 1992-02-11 | Chemical Research & Licensing Company | Hydroisomerization process |
| US4970191A (en) * | 1989-04-18 | 1990-11-13 | Aristech Chemical Corporation | Basic mixed oxide |
| US5153165A (en) * | 1991-05-09 | 1992-10-06 | Phillips Petroleum Company | Preparation of alkaline earth oxide catalysts |
| FR2733978B1 (en) * | 1995-05-11 | 1997-06-13 | Inst Francais Du Petrole | PROCESS AND INSTALLATION FOR THE CONVERSION OF OLEFINIC C4 AND C5 CUPS INTO ETHER AND PROPYLENE |
| FR2755130B1 (en) * | 1996-10-28 | 1998-12-11 | Inst Francais Du Petrole | NEW PROCESS FOR THE PRODUCTION OF ISOBUTENE AND PROPYLENE FROM FOUR-CARBON HYDROCARBON CUTS |
| EP0998976A1 (en) * | 1998-11-04 | 2000-05-10 | Engelhard Corporation | Star shaped alumina extrudates and catalyst based thereon |
| DE10013253A1 (en) * | 2000-03-17 | 2001-09-20 | Basf Ag | Production of propene and hexene from butenes in a raffinate II C4 fraction comprises reaction with ethene on a Group VIb, VIIb or VIII metal metathesis catalyst |
| US6727396B2 (en) * | 2001-01-25 | 2004-04-27 | Abb Lummus Global, Inc. | Process for the production of linear alpha olefins and ethylene |
| US6875901B2 (en) * | 2001-05-23 | 2005-04-05 | Abb Lummus Global Inc. | Olefin isomerization process |
| US6683019B2 (en) * | 2001-06-13 | 2004-01-27 | Abb Lummus Global Inc. | Catalyst for the metathesis of olefin(s) |
| US6777582B2 (en) * | 2002-03-07 | 2004-08-17 | Abb Lummus Global Inc. | Process for producing propylene and hexene from C4 olefin streams |
| FI118516B (en) * | 2003-03-14 | 2007-12-14 | Neste Oil Oyj | Process for the preparation of the catalyst |
| US7214841B2 (en) * | 2003-07-15 | 2007-05-08 | Abb Lummus Global Inc. | Processing C4 olefin streams for the maximum production of propylene |
| US7074976B2 (en) * | 2003-08-19 | 2006-07-11 | Equistar Chemicals, Lp | Propylene production |
| US7223895B2 (en) * | 2003-11-18 | 2007-05-29 | Abb Lummus Global Inc. | Production of propylene from steam cracking of hydrocarbons, particularly ethane |
| KR101159087B1 (en) * | 2003-12-12 | 2012-06-25 | 미쓰비시 가가꾸 가부시키가이샤 | Process for producing propylene |
| US8178737B2 (en) * | 2007-06-14 | 2012-05-15 | Lyondell Chemical Technology, L.P. | Propylene production |
| CN101827804A (en) | 2007-10-15 | 2010-09-08 | 巴斯夫欧洲公司 | Method for isomerizing olefins |
| CN102143929B (en) * | 2008-09-04 | 2014-12-03 | 鲁姆斯科技公司 | Olefin isomerization and metathesis catalyst |
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